Detergent tablet

ABSTRACT

A detergent tablet comprising a non-compressed, gelatinous portion, wherein the gelatinous portion comprising a thickening system and at least one detergent active. The thickening system preferably includes a non-aqueous diluent and a gelling agent and the detergent active is preferably selected from the group consisting of enzymes, surfactants, effervescing agents, bleaching agents, silver care agents, builders, and mixtures thereof. The non-compressed, gelatinous portion, may contain one, two or a plurality of non-compressed, gelatinous portions, all of which comprise a thickening system and at least one detergent active.

This application is a 371 of PCT/US98/23612 filed Nov. 5, 1998 whichclaims the benefit of U.S. Provisional Application No. 60/066,621 filedNov. 26, 1997 and U.S. Provisional Application No. 60/072,439 filed Jan.26, 1998.

TECHNICAL FIELD

The present invention relates to non-compressed detergent tablets.

BACKGROUND OF THE INVENTION

Detergent compositions in tablet form are known in the art. Detergentcompositions in tablet form hold several advantages over detergentcompositions in particulate or liquid form, such as ease of use andhandling, convenient dosing, ease of transportation and storage. Due tothese advantages, detergent compositions in tablet form are becomingincreasingly popular with consumers of detergent products.

Detergent tablets are most commonly prepared by pre-mixing thecomponents and forming the pre-mixed components into a tablet via theuse of a tablet press and compression of the components. However,traditional tablet compression processes have significant drawbacks,including but not limited to the fact that selected components of adetergent composition may be adversely affected by the compressionpressure in the tablet press. Accordingly, these selected componentswere not typically included in prior art detergent tablets withoutsustaining a loss in performance. In some cases, these selectedcomponents may even have become unstable or inactive as a result of thecompression.

In addition, as the components of the detergent composition arecompressed in the tablet press, they are brought into close proximitywith one another resulting in the reaction of selected component,instability, inactivity or exhaustion of the active form of thecomponents.

To avoid the above mentioned drawbacks, prior art detergent tablets haveattempted to separate components of the detergent composition that maypotentially react with each other when the detergent composition iscompressed into tablet form. Separation of the components has beenachieved by, for example, preparing multiple-layer tablets wherein thereactive components are contained in different layers of the tablet orencapsulation and coating of reactive components. These prior artmultiple-layer tablets are traditionally prepared using multiplecompression steps. Accordingly, layers of the tablet which are subjectedto more than one compression step may be subjected to a cumulative andpotentially greater overall compression pressure. In addition, anincrease in compression pressure of the tabletting press is known todecrease the rate of dissolution of the tablet with the effect that suchmultiple layer tablets may not dissolve satisfactorily in use. Nor isthere any significant variation in the dissolution rates of the multiplelayers.

Accordingly, the need remains for an improved detergent tablet which candeliver active detergent ingredients to a domestic wash process therebydelivering superior performance benefits.

SUMMARY OF THE INVENTION

This need is met by the present invention wherein a detergent tablethaving a non-compressed gelatinous body is provided. The tablet of thepresent invention provides a superior delivery mechanism for detergentcomponents. In addition, the detergent tablet of the present inventionprovides superior cleaning performance, particularly in domesticautomatic dishwashing machines over the tablets of the prior art.

According to a first embodiment of the present invention, a detergenttablet is provided. The tablet comprises a non-compressed, gelatinousbody, the gelatinous body comprising a thickening system and at leastone detergent active and wherein the gelatinous body is formulated sothat at least about 80% of the detergent active is delivered to the washwithin the first 5 minutes of a domestic wash process.

According to a second embodiment of the present invention, a detergenttablet is provided. The tablet comprises a non-compressed, gelatinousbody, the gelatinous body comprising a thickening system and at leastone detergent active and the detergent tablet has a dissolution rate ofgreater than about 0.33 g/min as determined using the SOTAX dissolutiontest method.

According to a third embodiment of the present invention, a detergenttablet is provided. The tablet comprises a non-compressed, gelatinousbody, which comprises:

i) a first non-compressed, gelatinous portion, the first gelatinousportion comprising a thickening system and at least one detergentactive; and

ii) a second non-compressed, gelatinous portion, the second gelatinousportion comprising a thickening system and at least one detergentactive; and wherein the first gelatinous body is formulated so that atleast about 80% of said detergent active is delivered to the wash withinthe first 5 minutes of a domestic wash process.

According to a fourth embodiment of the present invention, a detergenttablet is provided. The tablet comprises a non-compressed, gelatinousbody, which comprises:

i) a first non-compressed, gelatinous portion, the first gelatinousportion comprising a thickening system and at least one detergentactive; and

ii) a second non-compressed, gelatinous portion, the second gelatinousportion comprising a thickening system and at least one detergentactive; and wherein the detergent tablet is formulated so that at leastabout 80% of said detergent active is delivered to the wash within thefirst 5 minutes of a domestic wash process.

According to a fifth embodiment of the present invention, a detergenttablet is provided. The tablet comprises a non-compressed, gelatinousbody, which comprises a plurality of non-compressed, gelatinousportions, wherein each gelatinous portion comprises a thickening systemand at least one detergent active; and wherein at least one of saidplurality of non-compressed, gelatinous portions is formulated so thatat least about 80% of said detergent active is delivered to the washwithin the first 5 minutes of a domestic wash process.

According to a sixth embodiment of the present invention, a detergenttablet is provided. The tablet comprises a non-compressed, gelatinousbody, which comprises a plurality of non-compressed, gelatinousportions, wherein each gelatinous portion comprises a thickening systemand at least one detergent active; and wherein said detergent tablet isformulated so that at least about 80% of said detergent active isdelivered to the wash within the first 5 minutes of a domestic washprocess.

The detergent active in the detergent tablet, non-compressed, gelatinousbody or in any of the non-compressed, gelatinous portions may beselected from the group consisting of surfactants, enzymes, bleachingagents, effervescing agents, silver care agents, builders, silicates, pHcontrol agents or buffers, enzymes, alkalinity sources, colorants,perfume, lime soap dispersants, organic polymeric compounds includingpolymeric dye transfer inhibiting agents, crystal growth inhibitors,heavy metal ion sequestrants, metal ion salts, enzyme stabilizers,corrosion inhibitors, suds suppressers, solvents, fabric softeningagents, optical brighteners and hydrotropes and mixtures thereof, withenzymes and disrupting agents being the most preferred. When adisrupting agent is included, the disrupting agent is preferably a saltof carbonate or bicarbonate and an organic acid.

In alternative embodiments, the detergent tablet, non-compressed,gelatinous body or in any of the non-compressed, gelatinous portions maycontain at least about 15% suspended solids and more preferably at leastabout 40% of the gel portion is a suspended solid. The detergent tablet,non-compressed, gelatinous body or in any of the non-compressed,gelatinous portions may further includes a swelling/adsorbing agent.

The thickening system of the present invention preferably comprises amixture of a non-aqueous diluent or solvent and a gelling agent. Thegelling agent may be selected from the group consisting of castor oilderivatives, polyethylene glycol and mixtures thereof and is preferablypolyethylene glycol. The non-aqueous diluent may be selected from thegroup consisting of low molecular weight polyethylene glycols, glyceroland modified glycerols, propylene glycol, alkyleneglycol alkyl ethersand mixtures thereof and is preferably dipropyleneglycol butylether,propylene glycol or glycerol triacetate.

Accordingly, it is an object of the present invention to provide adetergent tablet having a non-compressed, gelatinous body or a pluralityof non-compressed, gelatinous portion. It is a further object of thepresent invention to provide a detergent tablet, non-compressed,gelatinous body or in any of the non-compressed, gelatinous portionswhich can quickly and efficiently deliver detergent actives to adomestic wash process. It is still further an object of the presentinvention to provide a detergent tablet, non-compressed, gelatinous bodyor a plurality of non-compressed, gelatinous portions which arepumpable, flowable gels at slightly elevated temperatures yet harden orthicken to maintain their form at ambient temperatures, particularlywhen shear is removed from the gel. These, and other objects, featuresand advantages of the present invention will be readily apparent to oneof ordinary skill in the art from the following detailed description andthe appended claims.

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All temperatures are in degrees Celsius (° C.)unless otherwise specified. All documents cited are in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention comprises a detergent tablet and in particular adetergent tablet for laundry or automatic dishwashing which has agelatinous body or a plurality of gelatinous portions which isnon-compressed. The use of the non-compressed, gelatinous body or aplurality of non-compressed, gelatinous portions provides a superiordelivery mechanism for detergent active agents into the domestic washprocess. The non-compressed, gelatinous body or a plurality ofnon-compressed, gelatinous portions provides unique properties of rapiddissolution or dispersion thereby providing for the earliest possibledelivery of detergent active agents into the domestic wash process.

Accordingly, by way of the present invention, active detergentcomponents of a detergent tablet previously adversely affected by thecompression pressure used to form the tablets may now be included in adetergent tablet. Examples of these components include bleaching agentsand enzymes. In addition, these active detergent components may beseparated from one another by having one or more compatible componentscontained in the any of the plurality of non-compressed, gelatinousportions and one or more compatible components contained in any of theplurality of non-compressed, gelatinous portions of the tablet. Examplesof components that may interact and may therefore require separationinclude bleaching agents, bleach activators or catalyst and enzymes;bleaching agents and bleach catalysts or activators; bleaching agentsand surfactants; alkalinity sources, perfumes and enzymes.

It may be advantageous to provide a plurality of non-compressed,gelatinous portions such that they dissolve in the wash water withdifferent dissolution rates. By controlling the rate of dissolution ofeach portion relative to one another, and by selection of the activedetergent components in the respective portions, their order of releaseinto the wash water can be controlled and the cleaning performance ofthe detergent tablet may be improved. For example it is often preferredthat enzymes are delivered to the wash prior to builders and/orbleaching agent and/or bleach activator. It may also be preferred that asource of alkalinity is released into the wash water more rapidly thanother components of the detergent tablet. It is also envisaged that itmay be advantageous to prepare a detergent tablet according to thepresent invention wherein the release of certain components of thetablet is delayed relative to other components.

It is possible for one or more detergent actives in a non-compressed,gelatinous portion to be delayed in its release. When the detergenttablet has two or more non-compressed, gelatinous portions at least onedetergent active, preferably one, may be delayed in its release for atleast five minutes, preferably seven minutes, into the wash solution. Itis also possible for the release of the detergent active to be delayeduntil the after wash rinse cycle, such as the after wash rinse cycle ina washing machine or in an automatic dishwashing machine. This delayedrelease allows for the addition of detergent actives which are usefulduring the rinse cycle such as surfactants, fabric softeners, bleaches,etc.

The tablet may also comprise non-compressed, gelatinous body or aplurality of non-compressed, gelatinous portions. For example, aplurality of compressed portions may be arranged in horizontal layers.Thus, there may be a non-compressed, gelatinous body or a plurality ofnon-compressed, gelatinous portions each comprising an active detergentcomponent and where different portions may comprise different activedetergent components or mixtures of components. Such a plurality ofnon-compressed, gelatinous portions may be advantageous, enabling atablet to be produced which has for example, a first and second andoptional subsequent portions so that they have different rates ofdissolution. Such performance benefits are achieved by selectivelydelivering active-detergent components into the wash water at differenttimes.

It is preferred that the detergent tablets, of the present invention befree from foul or noxious odors. If present such odors may be masked orremoved. This includes the addition of masking agents, perfumes, odorabsorbers, such as cyclodextrins, etc.

The detergent tablet may be transparent, opaque or any possible shade inbetween these two extremes. When there are more than one non-compressed,gel portion present in the detergent tablet it is possible for each ofthe gel portions to have the same or different degree of transparency,i.e. ranging from totally transparent to opaque. However, it ispreferred that they are different.

The detergent tablets described herein are preferably between 15 g and100 g in weight, more preferably between 18 g and 80 g in weight, evenmore preferably between 20 g and 60 g in weight. The detergent tabletdescribed herein that are suitable for use in automatic dishwashingmethods are most preferably between 20 g and 40 g in weight. Detergenttablets suitable for use in fabric laundering methods are mostpreferably between 40 g and 100 g, more preferably between 40 g and 80g, most preferably between 40 g and 65 g in weight.

The non-compressed, gelatinous body, of the detergent tablets describedherein can have a dissolution rate of faster than 0.33 g/min, preferablyfaster than 0.5 g/min, more preferably faster than 1.00 g/min, even morepreferably faster than 2.00 g/m, most preferably faster than 2.73 g/min.Dissolution rate is measured using the SOTAX dissolution test method.For the purposes of the present invention dissolution of detergenttablets is achieved using a SOTAX (tradename) machine; model number AT7available from SOTAX.

SOTAX Dissolution Test Method: The SOTAX machine consists of atemperature controlled waterbath with lid. 7 pots are suspended in thewater bath. 7 electric stirring rods are suspended from the underside ofthe lid, in positions corresponding to the position of the pots in thewaterbath. The lid of the waterbath also serves as a lid on the pots.

The SOTAX waterbath is filled with water and the temperature gauge setto 50° C. Each pot is then filled with 1 liter of deionised water andthe stirrer set to revolve at 250 rpm. The lid of the waterbath isclosed, allowing the temperature of the deionised water in the pots toequilibrate with the water in the waterbath for 1 hour.

The tablets are weighed and one tablet is placed in each pot, the lid isthen closed. The tablet is visually monitored until it completelydissolves. The time is noted when the tablet has completely dissolved.The dissolution rate of the tablet is calculated as the average weight(g) of tablet dissolved in deionised water per minute.

Gel Portion

The non-compressed, gelatinous body or the plurality of non-compressed,gelatinous portions comprises a thickening system and at least onedetergent active agent. The non-compressed, gelatinous body or theplurality of non-compressed, gelatinous portions is preferablyformulated such that the detergent active ingredient is essentiallycompletely delivered in a short period of time. The non-compressed,gelatinous body, at least one of the plurality of non-compressed,gelatinous portions or the detergent tablet can be formulated so that atleast about 80% of the detergent active is delivered to the wash of adomestic washing process within the first 5 minutes, more preferably atleast about 90% in the first 3 minutes and even more preferably about95% within the first 2 minutes as measured from the first point at whichthe tablet is completely immersed in water, particularly in cold watertemperatures, such as, e.g., 25° C. It is preferred that thenon-compressed, gelatinous body, at least one of the plurality ofnon-compressed, gelatinous portions or the detergent tablet be capableof dissolving in cold water, i.e. less than 30° C., preferably fromabout 10° C. to about 28° C. Thus, the tablet of the present inventionis particularly effective at delivering detergent actives in varyingwater temperatures including cold water.

Alternatively, the detergent can have a dissolution rate of faster than0.33 g/min, preferably faster than 0.5 g/min, more preferably fasterthan 1.00 g/min, even more preferably faster than 2.00 g/m, mostpreferably faster than 2.73 g/min. Dissolution rate is measured usingthe SOTAX dissolution test method. For the purposes of the presentinvention dissolution of detergent tablets is achieved using a SOTAX(tradename) machine; model number AT7 available from SOTAX.

The detergent tablet, the non-compressed, gelatinous body or any of theplurality of non-compressed, gelatinous portions may include solidingredients which are dispersed or suspended within the detergenttablet, the non-compressed, gelatinous body or any of the plurality ofnon-compressed, gelatinous portions. The solid ingredients aid in thecontrol of the viscosity of the non-compressed, gelatinous body, or anyof the plurality of non-compressed, gelatinous portions formulation inconjunction with the thickening system. In addition, solid ingredientsmay act to optionally disrupt the non-compressed, gelatinous body, orany of the plurality of non-compressed, gelatinous portions therebyaiding in dissolution of the detergent tablet, non-compressed,gelatinous body, or any of the plurality of non-compressed, gelatinousportions. When included, the detergent tablet, non-compressed,gelatinous body, or any of the plurality of non-compressed, gelatinousportions comprises at least about 15% solid ingredients, more preferablyat least about 30% solid ingredients and most preferably at least about40% solid ingredients. However, due to pumpability and other processingconcerns, the non-compressed, gelatinous body, or any of the pluralityof non-compressed, gelatinous portions of the present inventiontypically do not include more than about 90% solid ingredients.

The detergent tablet, non-compressed, gelatinous body, or any of theplurality of non-compressed, gelatinous portions may additionallycontain a drying agent. Any, conventional drying agent may be used. SeeVogels Text book of Practical Organic Chemistry, 5^(th) Edition (1989)Longman Scientific & Technical, pp. 165-168, incorporated herein byreference. For example, suitable drying agents are anhydrous CaSO₄,anhydrous Na₂SO₄, sodium sulfite, calcium chloride and MgSO₄. Theselection of suitable drying agents may depend on the end use of thetablet. A drying agent for a detergent tablet for an automaticdishwashing composition for low temperatures is preferably sodiumsulfite or calcium chloride but anhydrous CaSO₄, may be used for higheruse temperatures. When present drying agents will range from about 0.1%to about 15%, more preferably from about 0.1% to about 10%, even morepreferably from about 0.5% to about 7%, by weight of the tablet.

In a preferred embodiment the detergent tablet, non-compressed,gelatinous body, or any of the plurality of non-compressed, gelatinousportions are coated with a coating layer. The coating layer preferablycomprises a material that becomes solid on contacting the detergenttablet, non-compressed, gelatinous body, or any of the plurality ofnon-compressed, gelatinous portions within preferably less than 15minutes, more preferably less than 10 minutes, even more preferably lessthan 5 minutes, most preferably less than 60 seconds. Preferably thecoating layer is water-soluble. Preferred coating layers comprisematerials selected from the group consisting of fatty acids, alcohols,diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylicacid, polyvinyl acetate (PVA), polyvinyl pyrrolidone (PVP), polyaceticacid, polyethylene glycol (PEG) and mixtures thereof. Preferredcarboxylic or dicarboxylic acids preferably comprise an even number ofcarbon atoms. Preferably carboxylic or dicarboxylic acids comprise atleast 4, more preferably at least 6, even more preferably at least 8carbon atoms, most preferably between 8 and 13 carbon atoms. Preferreddicarboxylic acids include adipic acid, suberic acid, azelaic acid,subacic acid, undecanedioic acid, dodecandioic acid, tridecanedioic andmixtures thereof Preferred fatty acids are those having a carbon chainlength of from C12 to C22, most preferably from C18 to C22. The coatinglayer may also preferably comprise a disrupting agent. Where present thecoating layer generally present at a level of at least about 0.05%, morepreferably at least about 0.1%, even more preferably at least about 1%,even more preferably still at least about 2% or even at least about 5%of the detergent tablet.

Thickening System

As noted earlier, the detergent tablet of the present inventioncomprises thickening system in the non-compressed, gelatinous body, andin the plurality of non-compressed, gelatinous portions to provide theproper viscosity or thickness of the gel portion. The thickening systemtypically comprises a non-aqueous liquid diluent and an organic orpolymeric gelling additive.

a) Liquid Diluent

The term “solvent” or “diluent” is used herein to connote the liquidportion of the thickening system. While some of the essential and/oroptional components of the compositions herein may actually dissolve inthe “solvent”-containing phase, other components will be present asparticulate material dispersed within the “solvent”-containing phase.Thus the term “solvent” is not meant to require that the solventmaterial be capable of actually dissolving all of the detergentcomposition components added thereto. Suitable types of solvents usefulin the non-aqueous thickening systems herein include alkylene glycolmono lower alkyl ethers, propylene glycols, ethoxylated or propoxylatedethylene or propylene, glycerol esters, glycerol triacetate, lowermolecular weight polyethylene glycols, lower molecular weight methylesters and amides, and the like.

A preferred type of non-aqueous solvent for use herein comprises themono-, di-, tri-, or tetra- C₂-C₃ alkylene glycol mono C₂-C₆ alkylethers. The specific examples of such compounds include diethyleneglycol monobutyl ether, tetraethylene glycol monobutyl ether,dipropylene glycol monoethyl ether, and dipropylene glycol monobutylether. Diethylene glycol monobutyl ether and dipropylene glycolmonobutyl ether are especially preferred. Compounds of the type havebeen commercially marketed under the tradenames Dowanol, Carbitol, andCellosolve.

Another preferred type of non-aqueous solvent useful herein comprisesthe lower molecular weight polyethylene glycols (PEGs). Such materialsare those having molecular weights of at least about 150. PEGs ofmolecular weight ranging from about 200 to 600 are most preferred.

Yet another preferred type of non-aqueous solvent comprises lowermolecular weight methyl esters. Such materials are those of the generalformula: R¹—C(O)—OCH₃ wherein R¹ ranges from 1 to about 18. Examples ofsuitable lower molecular weight methyl esters include methyl acetate,methyl propionate, methyl octanoate, and methyl dodecanoate.

The non-aqueous organic solvent(s) employed should, of course, becompatible and non-reactive with other composition components, e.g.,enzymes, used in the detergent tablets herein. Such a solvent componentwill generally be utilized in an amount of from about 10% to about 60%by weight. More preferably, the non-aqueous, low-polarity organicsolvent will comprise from about 20% to about 50%,most preferably fromabout 30% to about 50% by weight.

b) Gelling Additive

As noted earlier, a gelling agent or additive is added to the nonaqueous solvent of the present invention to complete the thickeningsystem. To achieve the required phase stability and acceptable rheologyof the gel, the organic gelling agent is generally present to the extentof a ratio of solvent to gelling agent in thickening system typicallyranging from about 99:1 to about 1:1. More preferably, the ratios rangefrom about 19:1 to about 4:1.

The preferred gelling agents of the present invention are selected fromcastor oil derivatives, polyethylene glycol, sorbitols and relatedorganic thixatropes, organoclays, cellulose and cellulose derivatives,pluronics, stearates and stearate derivatives, sugar/gelatincombination, starches, glycerol and derivatives thereof, organic acidamides such as N-lauryl-L-glutamic acid di-n-butyl amide, polyvinylpyrrolidone and mixtures thereof.

The preferred gelling agents include castor oil derivatives. Castor oilis a naturally occurring triglyceride obtained from the seeds of RicinusCommunis, a plant which grows in most tropical or subtropical areas. Theprimary fatty acid moiety in the castor oil triglyceride is ricinoleicacid (12-hydroxy oleic acid). It accounts for about 90% of the fattyacid moieties. The balance consists of dihydroxystearic, palmitic,stearic, oleic, linoleic, linolenic and eicosanoic moieties.Hydrogenation of the oil (e.g., by hydrogen under pressure) converts thedouble bonds in the fatty acid moieties to single bonds, thus“hardening” the oil. The hydroxyl groups are unaffected by thisreaction.

The resulting hydrogenated castor oil, therefore, has an average ofabout three hydroxyl groups per molecule. It is believed that thepresence of these hydroxyl groups accounts in large part for theoutstanding structuring properties which are imparted to the gelcompared to similar liquid detergent compositions which do not containcastor oil with hydroxyl groups in their fatty acid chains. For use inthe compositions of the present invention the castor oil should behydrogenated to an iodine value of less than about 20, and preferablyless than about 10. Iodine value is a measure of the degree ofunsaturation of the oil and is measured by the “Wijis Method,” which iswell-known in the art. Unhydrogenated castor oil has an iodine value offrom about 80 to 90.

Hydrogenated castor oil is a commercially available commodity beingsold, for example, in various grades under the trademark CASTORWAX.RTM.by NL Industries, Inc., Highstown, N.J. Other Suitable hydrogenatedcastor oil derivatives are Thixcin R, Thixcin E, Thixatrol ST, Perchem Rand Perchem ST, made by Rheox, Laporte. Especially preferred isThixatrol ST.

Polyethylene glycols when employed as gelling agents, rather thansolvents, have a molecular weight range of from about 2000 to about30000, preferably about 4000 to about 12000, more preferably about 6000to about 10000.

Cellulose and cellulose derivatives when employed in the presentinvention preferably include: i) Cellulose acetate and Cellulose acetatephthalate (CAP); ii) Hydroxypropyl Methyl Cellulose (HPMC);iii)Carboxymethylcellulose (CMC); and mixtures thereof. Thehydroxypropyl methylcellulose polymer preferably has a number averagemolecular weight of about 50,000 to 125,000 and a viscosity of a 2 wt. %aqueous solution at 25° C. (ADTMD2363) of about 50,000 to about 100,000cps. An especially preferred hydroxypropyl cellulose polymer isMethocel® J75MS-N wherein a 2.0 wt. % aqueous solution at 25° C. has aviscosity of about 75,000 cps.

The sugar may be any monosaccharide (e.g. glucose), disaccharide (e.g.sucrose or maltose) or polysaccharide. The most preferred sugar iscommonly available sucrose. For the purposes of the present inventiontype A or B gelatin may be used, available from for example Sigma. TypeA gelatin is preferred since it has greater stability in alkalineconditions in comparison to type B. Preferred gelatin also has a bloomstrength of between 65 and 300, most preferably between 75 and 100.

The non-compressed, gelatinous body, or any of the plurality ofnon-compressed, gelatinous portions of the present invention may includea variety of other ingredients in addition to the thickening agent asherein before described and the detergent active disclosed in moredetail below. Ingredients such as perfumes and dyes may be included aswell as structure modifying agents. Structure modifying agents includevarious polymers and mixtures of polymers included polycarboxylates,carboxymethylcelluloses and starches to aid in adsorption of excesssolvent and/or reduce or prevent “bleeding” or leaking of the solventfrom the gel portion, reduce shrinkage or cracking of the gel portion oraid in the dissolution or breakup of the gel portion in the wash. Inaddition, hardness modifying agents may incorporated into the thickeningsystem to adjust the hardness of the non-compressed, gelatinous body, orany of the plurality of non-compressed, gelatinous portions if desired.These hardness control agents are typically selected from variouspolymers, such as polyethylene glycol's, polyethylene oxide,polyvinylpyrrolidone, polyvinyl alcohol, hydroxystearic acid andpolyacetic acid and when included are typically employed in levels ofless than about 20% and more preferably less than about 10% by weight ofthe solvent in the thickening system. For example, hardening agents,such as high molecular weight PEG, preferably of a molecular weight from10,000 to 20,000 or possibly even higher molecular weight, can be addedto decrease the hardening time of the non-compressed, non-encapsulatingportion. Alternatively, water soluble polymeric materials such as of lowmolecular weight polyethylene glycols may be added to the mould to forman intermediate barrier layer prior to addition of the non-compressed,non-encapsulating portion when it is a gel. This speeds cooling andhardening of the gel by the melting/mixing of the water solublepolymeric material when the gel is added to the at least one mould. Inaddition, the intermediate layer may act as a barrier to preventingredients from the gel mixing or bleeding into the compressed portion.

Addition of an alkaline material, such as sodium or potassium hydroxidecan also speed in hardening of the non-compressed, non-encapsulatingportion when it is a gel. Preferably, these alkaline materials would beadded to the mould before the addition of the gel. However, inalternative systems, the alkaline material may be added to the gelcomposition. These alkaline materials also have the advantage of actingas an additional alkalinity source that is discrete and would be slowerdissolving and hence have a minimal impact on any effervescence systempresent in the non-compressed, non-encapsulating portion yet provide analkalinity boost in the wash.

The non-compressed, gelatinous body, or any of the plurality ofnon-compressed, gelatinous portions of the present invention isformulated so that the non-compressed, gelatinous body, or any of theplurality of non-compressed, gelatinous portions is pumpable andflowable at slightly elevated temperatures of around 30° C. or greaterto allow increased flexibility in producing the detergent tablet, butbecomes highly viscous or hardens at ambient temperatures so that theshape of the detergent tablet, non-compressed, gelatinous body, or anyof the plurality of non-compressed, gelatinous portions is maintainedthrough shipping and handling of the detergent tablet. Such hardening ofthe detergent tablet, non-compressed, gelatinous body, or any of theplurality of non-compressed, gelatinous portions may achieved, forexample, by (i) cooling to below the flowable temperature of the gelportion or the removal of shear; (ii) by solvent transfer, for exampleeither to the atmosphere of the compressed body portion; or by (iii) bypolymerisation of the gelling agent. Preferably, the non-compressed,gelatinous body, or any of the plurality of non-compressed, gelatinousportions is formulated such that the non-compressed, gelatinous body, orany of the plurality of non-compressed, gelatinous portions hardens tosufficiently so that the maximum force needed to push a probe into thedetergent tablet, non-compressed, gelatinous body, or any of theplurality of non-compressed, gelatinous portions preferably ranges fromabout 0.5N to about 40N. This force may be characterised by measuringthe maximum force needed to push a probe, fitted with a strain gauge, aset distance into the gel portion. The set distance may be between about40 and about 80% of the total detergent tablet, non-compressed,gelatinous body, or any of the plurality of non-compressed, gelatinousportions depth. This force can be measured on a QTS 25 tester, using aprobe of 5 mm diameter. Typical forces measured are in the range of 1Nto 25N.

Additionally, it is preferred that when a 48 hour old tablet isinverted, at ambient conditions, for 10 minutes, more preferably 30minutes, even more preferably 2 hours, the non-compressed, gelatinousbody, or any of the plurality of non-compressed, gelatinous portions donot drip or separate form the rest of the detergent tablet.

Detergent Actives

The detergent tablets described herein may include a variety ofdifferent detergent active components including, but not limited to,surfactants, enzymes, bleaching agents, effervescing agents, silver careagents, builders, silicates, pH control agents or buffers, enzymes,alkalinity sources, colorants, perfume, lime soap dispersants, organicpolymeric compounds including polymeric dye transfer inhibiting agents,crystal growth inhibitors, heavy metal ion sequestrants, metal ionsalts, enzyme stabilizers, corrosion inhibitors, suds suppressers,solvents, fabric softening agents, optical brighteners and hydrotropesand mixtures thereof.

Surfactants

Surfactants are preferred detergent active components of thecompositions described herein. Suitable surfactants are selected fromanionic, cationic, nonionic ampholytic and zwitterionic surfactants andmixtures thereof. Automatic dishwashing machine products should be lowfoaming in character and thus the foaming of the surfactant system foruse in dishwashing methods must be suppressed or more preferably be lowfoaming, typically nonionic in character. Sudsing caused by surfactantsystems used in laundry cleaning methods need not be suppressed to thesame extent as is necessary for dishwashing.

A typical listing of anionic, nonionic, ampholytic and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,929,678 issued to Laughlin and Heuring on Dec., 30, 1975. A list ofsuitable cationic surfactants is given in U.S. Pat. No. 4,259,217 issuedto Murphy on Mar. 31, 1981. A listing of surfactants typically includedin automatic dishwashing detergent compositions is given for example, inEP-A-0414 549 and PCT Applications Nos. WO 93/08876 and WO 93/08874.

Detersive surfactants, when included in the fully-formulated detergentcompositions afforded by the present invention comprises preferably atleast about 0.01%, more preferably from about 0.5% to about 50%, byweight of detergent composition depending upon the particularsurfactants used and the desired effects. In a highly preferredembodiment, the detersive surfactant comprises from about 0.5% to about20% by weight of the composition.

The detersive surfactant can be nonionic, anionic, ampholytic,zwitterionic, or cationic. Mixtures of these surfactants can also beused. Preferred detergent compositions comprise anionic detersivesurfactants or mixtures of anionic surfactants with other surfactants,especially nonionic surfactants.

Nonionic Surfactants

Particularly preferred surfactants in the preferred automaticdishwashing compositions (ADD) of the present invention are low foamingnonionic surfactants (LFNI). LFNI may be present in amounts from 0.01%to about 10% by weight, preferably from about 0.1% to about 10%, andmost preferably from about 0.25% to about 4%. LFNIs are most typicallyused in ADDs on account of the improved water-sheeting action(especially from glass) which they confer to the ADD product. They alsoencompass non-silicone, nonphosphate polymeric materials furtherillustrated hereinafter which are known to defoam food soils encounteredin automatic dishwashing.

Preferred LFNIs include nonionic alkoxylated surfactants, especiallyethoxy-lates derived from primary alcohols, and blends thereof with moresophisticated surfactants, such as thepolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers. The PO/EO/PO polymer-type surfactants are well-known tohave foam suppressing or defoaming action, especially in relation tocommon food soil ingredients such as egg.

The invention encompasses preferred embodiments wherein LFNI is present,and wherein this component is solid at about 95° F. (35° C.), morepreferably solid at about 77° F. (25° C.). For ease of manufacture, apreferred LFNI has a melting point between about 77° F. (25° C.) andabout 140° F. (60° C.), more preferably between about 80° F. (26.6° C.)and 110° F. (43.3° C.).

In a preferred embodiment, the LFNI is an ethoxylated surfactant derivedfrom the reaction of a monohydroxy alcohol or alkylphenol containingfrom about 8 to about 20 carbon atoms, with from about 6 to about 15moles of ethylene oxide per mole of alcohol or alkyl phenol on anaverage basis.

A particularly preferred LFNI is derived from a straight chain fattyalcohol containing from about 16 to about 20 carbon atoms (C₁₆-C₂₀alcohol), preferably-a C₁₈ alcohol, condensed with an average of fromabout 6 to about 15 moles, preferably from about 7 to about 12 moles,and most preferably from about 7 to about 9 moles of ethylene oxide permole of alcohol. Preferably the ethoxylated nonionic surfactant soderived has a narrow ethoxylate distribution relative to the average.

The LFNI can optionally contain propylene oxide in an amount up to about15% by weight. Other preferred LFNI surfactants can be prepared by theprocesses described in U.S. Pat. No. 4,223,163, issued Sep. 16, 1980,Builloty, incorporated herein by reference

Highly preferred ADDs herein wherein the LFNI is present make use ofethoxylated monohydroxy alcohol or alkyl phenol and additionallycomprise a polyoxyethylene, polyoxypropylene block polymeric compound;the ethoxylated monohydroxy alcohol or alkyl phenol fraction of the LFNIcomprising from about 20% to about 100%, preferably from about 30% toabout 70%, of the total LFNI.

Suitable block polyoxyethylene-polyoxypropylene polymeric compounds thatmeet the requirements described hereinbefore include those based onethylene glycol, propylene glycol, glycerol, trimethylolpropane andethylenediamine as initiator reactive hydrogen compound. Polymericcompounds made from a sequential ethoxylation and propoxylation ofinitiator compounds with a single reactive hydrogen atom, such as C₁₂₋₁₈aliphatic alcohols, do not generally provide satisfactory suds controlin the instant ADDs. Certain of the block polymer surfactant compoundsdesignated PLURONIC® and TETRONIC® by the BASF-Wyandotte Corp.,Wyandotte, Mich., are suitable in ADD compositions of the invention.

A particularly preferred LFNI contains from about 40% to about 70% of apolyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blendcomprising about 75%, by weight of the blend, of a reverse blockco-polymer of polyoxyethylene and polyoxypropylene containing 17 molesof ethylene oxide and 44 moles of propylene oxide; and about 25%, byweight of the blend, of a block co-polymer of polyoxyethylene andpolyoxypropylene initiated with trimethylolpropane and containing 99moles of propylene oxide and 24 moles of ethylene oxide per mole oftrimethylolpropane.

Suitable for use as LFNI in the ADD compositions are those LFNI havingrelatively low cloud points and high hydrophilic-lipophilic balance(HLB). Cloud points of 1% solutions in water are typically below about32° C. and preferably lower, e.g., 0° C., for optimum control of sudsingthroughout a full range of water temperatures.

LFNIs which may also be used include those POLY-TERGENT® SLF-18 nonionicsurfactants from Olin Corp., and any biodegradable LFNI having themelting point properties discussed hereinabove.

These and other nonionic surfactants are well known in the art, beingdescribed in more detail in Kirk Othmner's Encyclopedia of ChemicalTechnology, 3rd Ed., Vol. 22, pp. 360-379, “Surfactants and DetersiveSystems”, incorporated by reference herein.

Preferred are ADD compositions comprising mixed surfactants wherein thesudsing (absent any silicone suds controlling agent) is less than 2inches, preferably less than 1 inch, as determined by the disclosurebelow.

The equipment useful for these measurements are: a Whirlpool Dishwasher(model 900) equipped with clear plexiglass door, IBM computer datacollection with Labview and Excel Software, proximity sensor (NewarkCorp.—model 95F5203) using SCXI interface, and a plastic ruler.

The data is collected as follows. The proximity sensor is affixed to thebottom dishwasher rack on a metal bracket. The sensor faces downwardtoward the rotating dishwasher arm on the bottom of the machine(distance approximately 2 cm. from the rotating arm). Each pass of therotating arm is measured by the proximity sensor and recorded. Thepulses recorded by the computer are converted to rotations per minute(RPM) of the bottom arm by counting pulses over a 30 second interval.The rate of the arm rotation is directly proportional to the amount ofsuds in the machine and in the dishwasher pump (i.e., the more sudsproduced, the slower the arm rotation).

The plastic ruler is clipped to the bottom rack of the dishwasher andextends to the floor of the machine. At the end of the wash cycle, theheight of the suds is measured using the plastic ruler (viewed throughthe clear door) and recorded as suds height.

The following procedure is followed for evaluating ADD compositions forsuds production as well as for evaluating nonionic surfactants forutility. (For separate evaluation of nonionic surfactant, a base ADDformula, such as Cascade powder, is used along with the nonionicsurfactants which are added separately in glass vials to the dishwashingmachine.)

First, the machine is filled with water (adjust water for appropriatetemperature and hardness) and proceed through a rinse cycle. The RPM ismonitored throughout the cycle (approximately 2 min.) without any ADDproduct (or surfactants) being added (a quality control check to ensurethe machine is functioning properly). As the machine begins to fill forthe wash cycle, the water is again adjusted for temperature andhardness, and then the ADD product is added to the bottom of the machine(in the case of separately evaluated surfactants, the ADD base formulais first added to the bottom of the machine then the surfactants areadded by placing the surfactant-containing glass vials inverted on thetop rack of the machine). The RPM is then monitored throughout the washcycle. At the end of the wash cycle, the suds height is recorded usingthe plastic ruler. The machine is again filled with water (adjust waterfor appropriate temperature and hardness) and runs through another rinsecycle. The RPM is monitored throughout this cycle.

An average RPM is calculated for the 1st rinse, main wash, and finalrinse. The % RPM efficiency is then calculated by dividing the averageRPM for the test surfactants into the average RPM for the control system(base ADD formulation without the nonionic surfactant). The RPMefficiency and suds height measurements are used to dimension theoverall suds profile of the surfactant.

Nonionic Ethoxylated Alcohol Surfactant

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom 1 to 25 moles of ethylene oxide are suitable for use herein. Thealkyl chain of the aliphatic alcohol can either be straight or branched,primary or secondary, and generally contains from 6 to 22 carbon atoms.Particularly preferred are the condensation products of alcohols havingan alkyl group containing from 8 to 20 carbon atoms with from 2 to 10moles of ethylene oxide per mole of alcohol.

End-capped Alkyl Alkoxylate Surfactant

A suitable endcapped alkyl alkoxylate surfactant is the epoxy-cappedpoly(oxyalkylated) alcohols represented by the formula:

R₁O[CH₂CH(CH₃)O]_(x)[CH₂CH₂O]_(y)[CH₂CH(OH)R₂]  (I)

wherein R₁ is a linear or branched, aliphatic hydrocarbon radical havingfrom 4 to 18 carbon atoms; R₂ is a linear or branched aliphatichydrocarbon radical having from 2 to 26 carbon atoms; x is an integerhaving an average value of from 0.5 to 1.5, more preferably 1; and y isan integer having a value of at least 15, more preferably at least 20.

Preferably, the surfactant of formula I, at least 10 carbon atoms in theterminal epoxide unit [CH₂CH(OH)R₂]. Suitable surfactants of formula I,according to the present invention, are Olin Corporation's POLY-TERGENT®SLF-18B nonionic surfactants, as described, for example, in WO 94/22800,published Oct. 13, 1994 by Olin Corporation.

Ether-capped Poly(oxyalkylated) Alcohols

Preferred surfactants for use herein include ether-cappedpoly(oxyalkylated) alcohols having the formula:

R¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR²

wherein R¹ and R² are linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbonatoms; R³ is H, or a linear aliphatic hydrocarbon radical having from 1to 4 carbon atoms; x is an integer having an average value from 1 to 30,wherein when x is 2 or greater R³ may be the same or different and k andj are integers having an average value of from 1 to 12, and morepreferably 1 to 5.

R¹ and R² are preferably linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbonatoms with 8 to 18 carbon atoms being most preferred. H or a linearaliphatic hydrocarbon radical having from 1 to 2 carbon atoms is mostpreferred for R³. Preferably, x is an integer having an average value offrom 1 to 20, more preferably from 6 to 15.

As described above, when, in the preferred embodiments, and x is greaterthan 2, R³ may be the same or different. That is, R³ may vary betweenany of the alklyeneoxy units as described above. For instance, if x is3, R³ may be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) andmay vary in order of (EO)(PO)(EO), (EO)(EO)(PO); (EO)(EO)(EO);(PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO). Of course, the integerthree is chosen for example only and the variation may be much largerwith a higher integer value for x and include, for example, multiple(EO) units and a much small number of (PO) units.

Particularly preferred surfactants as described above include those thathave a low cloud point of less than 20° C. These low cloud pointsurfactants may then be employed in conjunction with a high cloud pointsurfactant as described in detail below for superior grease cleaningbenefits.

Most preferred ether-capped poly(oxyalkylated) alcohol surfactants arethose wherein k is 1 and j is 1 so that the surfactants have theformula:

R¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR²

where R¹, R² and R³ are defined as above and x is an integer with anaverage value of from 1 to 30, preferably from 1 to 20, and even morepreferably from 6 to 18. Most preferred are surfactants wherein R¹ andR² range from 9 to 14, R³ is H forming ethyleneoxy and x ranges from 6to 15.

The ether-capped poly(oxyalkylated) alcohol surfactants comprise threegeneral components, namely a linear or branched alcohol, an alkyleneoxide and an alkyl ether end cap. The alkyl ether end cap and thealcohol serve as a hydrophobic, oil-soluble portion of the moleculewhile the alkylene oxide group forms the hydrophilic, water-solubleportion of the molecule.

These surfactants exhibit significant improvements in spotting andfilming characteristics and removal of greasy soils, when used inconjunction with high cloud point surfactants, relative to conventionalsurfactants.

Generally speaking, the ether-capped poly(oxyalkylene) alcoholsurfactants of the present invention may be produced by reacting analiphatic alcohol with an epoxide to form an ether which is then reactedwith a base to form a second epoxide. The second epoxide is then reactedwith an alkoxylated alcohol to form the novel compounds of the presentinvention. Examples of methods of preparing the ether-cappedpoly(oxyalkylated) alcohol surfactants are described below:

Preparation of C_(12/14) Alkyl Glycidyl Ether

A C_(12/14) fatty alcohol (100.00 g, 0.515 mol.) and tin (IV) chloride(0.58 g, 2.23 mmol, available from Aldrich) are combined in a 500 mLthree-necked round-bottomed flask fitted with a condenser, argon inlet,addition funnel, magnetic stirrer and internal temperature probe. Themixture is heated to 60° C. Epichlorhydrin (47.70 g, 0.515 mol,available from Aldrich) is added dropwise so as to keep the temperaturebetween 60-65° C. After stirring an additional hour at 60° C., themixture is cooled to room temperature. The mixture is treated with a 50%solution of sodium hydroxide (61.80 g, 0.773 mol, 50%) while beingstirred mechanically. After addition is completed, the mixture is heatedto 90° C. for 1.5 h, cooled, and filtered with the aid of ethanol. Thefiltrate is separated and the organic phase is washed with water (100mL), dried over MgSO₄, filtered, and concentrated. Distillation of theoil at 100-120° C. (0.1 mm Hg) providing the glycidyl ether as an oil.

Preparation of C_(12/14) Alkyl-C_(9/11) Ether Capped Alcohol Surfactant

Neodol® 91-8 (20.60 g, 0.0393 mol ethoxylated alcohol available from theShell chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) arecombined in a 250 mL three-necked round-bottomed flask fitted with acondenser, argon inlet, addition funnel, magnetic stirrer and internaltemperature probe. The mixture is heated to 60° C. at which pointC_(12/14) alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwiseover 15 min. After stirring for 18 h at 60° C., the mixture is cooled toroom temperature and dissolved in an equal portion of dichloromethane.The solution is passed through a 1 inch pad of silica gel while elutingwith dichloromethane. The filtrate is concentrated by rotary evaporationand then stripped in a kugelrohr oven (100° C., 0.5 mm Hg) to yield thesurfactant as an oil.

For more details on these and other suitable nonionic surfactants seeU.S. patent Ser. Nos. 60/054,702, 60/054,688 and 60/057,025 all of whichare incorporated herein by reference.

Nonionic Ethoxylated/propoxylated Fatty Alcohol Surfactant

The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixedethoxylated/propoxylated fatty alcohols are suitable surfactants for useherein, particularly where water soluble. Preferably the ethoxylatedfatty alcohols are the C₁₀-C₁₈ ethoxylated fatty alcohols with a degreeof ethoxylation of from 3 to 50, most preferably these are the C₁₂-C₁₈ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.Preferably the mixed ethoxylated/propoxylated fatty alcohols have analkyl chain length of from 10 to 18 carbon atoms, a degree ofethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to10.

Nonionic EO/PO Condensates with Propylene Glycol

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol aresuitable for use herein. The hydrophobic portion of these compoundspreferably has a molecular weight of from 1500 to 1800 and exhibitswater insolubility. Examples of compounds of this type include certainof the commercially-available Pluronic™ surfactants, marketed by BASF.

Nonionic EO Condensation Products with Propylene Oxide/ethylene DiamineAdducts

The condensation products of ethylene oxide with the product resultingfrom the reaction of propylene oxide and ethylenediamine are suitablefor use herein. The hydrophobic moiety of these products consists of thereaction product of ethylenediamine and excess propylene oxide, andgenerally has a molecular weight of from 2500 to 3000. Examples of thistype of nonionic surfactant include certain of the commerciallyavailable Tetronic™ compounds, marketed by BASF.

Mixed Nonionic Surfactant System

In a preferred embodiment of the present invention the detergent tabletcomprises a mixed nonionic surfactant system comprising at least one lowcloud point nonionic surfactant and at least one high cloud pointnonionic surfactant.

“Cloud point”, as used herein, is a well known property of nonionicsurfactants which is the result of the surfactant becoming less solublewith increasing temperature, the temperature at which the appearance ofa second phase is observable is referred to as the “cloud point” (SeeKirk Othmer's Encyclopedia of Chemical Technology, 3^(rd) Ed. Vol. 22,pp. 360-379).

As used herein, a “low cloud point” nonionic surfactant is defined as anonionic surfactant system ingredient having a cloud point of less than30° C., preferably less than 20° C., and most preferably less than 10°C. Typical low cloud point nonionic surfactants include nonionicalkoxylated surfactants, especially ethoxylates derived from primaryalcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene(PO/EO/PO) reverse block polymers. Also, such low cloud point nonionicsurfactants include, for example, ethoxylated-propoxylated alcohol(e.g., Olin Corporation's Poly-Tergent® SLF18), epoxy-cappedpoly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent®SLF18B series of nonionics, as described, for example, in WO 94/22800,published Oct. 13, 1994 by Olin Corporation)and the ether-cappedpoly(oxyalkylated) alcohol surfactants.

Nonionic surfactants can optionally contain propylene oxide in an amountup to 15% by weight. Other preferred nonionic surfactants can beprepared by the processes described in U.S. Pat. No. 4,223,163, issuedSep. 16, 1980, Builloty, incorporated herein by reference.

Low cloud point nonionic surfactants additionally comprise apolyoxyethylene, polyoxypropylene block polymeric compound. Blockpolyoxyethylene-polyoxypropylene polymeric compounds include those basedon ethylene glycol, propylene glycol, glycerol, trimethylolpropane andethylenediamine as initiator reactive hydrogen compound. Certain of theblock polymer surfactant compounds designated PLURONIC®, REVERSEDPLURONIC®, and TETRONIC ® by the BASF-Wyandotte Corp., Wyandotte, Mich.,are suitable in ADD compositions of the invention. Preferred examplesinclude REVERSED PLURONIC® 25R2 and TETRONIC® 702, Such surfactants aretypically useful herein as low cloud point nonionic surfactants.

As used herein, a “high cloud point” nonionic surfactant is defined as anonionic surfactant system ingredient having a cloud point of greaterthan 40° C., preferably greater than 50° C., and more preferably greaterthan 60° C. Preferably the nonionic surfactant system comprises anethoxylated surfactant derived from the reaction of a monohydroxyalcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on anaverage basis. Such high cloud point nonionic surfactants include, forexample, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5(supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

It is also preferred for purposes of the present invention that the highcloud point nonionic surfactant further have a hydrophile-lipophilebalance (“HLB”; see Kirk Othmer hereinbefore) value within the range offrom 9 to 15, preferably 11 to 15. Such materials include, for example,Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (suppliedby Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

Another preferred high cloud point nonionic surfactant is derived from astraight or preferably branched chain or secondary fatty alcoholcontaining from 6 to 20 carbon atoms (C₆-C₂₀ alcohol), includingsecondary alcohols and branched chain primary alcohols. Preferably, highcloud point nonionic surfactants are branched or secondary alcoholethoxylates, more preferably mixed C9/11 or C11/15 branched alcoholethoxylates, condensed with an average of from 6 to 15 moles, preferablyfrom 6 to 12 moles, and most preferably from 6 to 9 moles of ethyleneoxide per mole of alcohol. Preferably the ethoxylated nonionicsurfactant so derived has a narrow ethoxylate distribution relative tothe average.

In a preferred embodiment the detergent tablet comprising such a mixedsurfactant system also comprises an amount of water-soluble salt toprovide conductivity in deionised water measured at 25° C. greater than3 milli Siemens/cm, preferably greater than 4 milli Siemens/cm, mostpreferably greater than 4.5 milli Siemens/cm.

In another preferred embodiment the mixed surfactant system dissolves inwater having a hardness of 1.246 mmol/L in any suitable cold-fillautomatic dishwasher to provide a solution with a surface tension ofless than 4 Dynes/cm² at less than 45° C., preferably less than 40° C.,most preferably less than 35° C.

In another preferred embodiment the high cloud point and low cloud pointsurfactants of the mixed surfactant system are separated such that oneof either the high cloud point or low cloud point surfactants is presentin a first matrix and the other is present in a second matrix. For thepurposes of the present invention, the first matrix may be a firstparticulate and the second matrix may be a second particulate. Asurfactant may be applied to a particulate by any suitable known method,preferably the surfactant is sprayed onto the particulate. In apreferred aspect the first matrix is the compressed portion and thesecond matrix is the non-compressed portion of the detergent tablet ofthe present invention. Preferably the low cloud point surfactant ispresent in the compressed portion and the high cloud point surfactant ispresent in the non-compressed portion of the detergent tablet of thepresent invention.

Branched Alkyl Alkoxylate Surfactants

Also suitable are the branched nonionic surfactants disclosed inco-pending U.S. patent application Ser. No. 60/031,917 which continuedas U.S. application Ser. No. 09/170424, now U.S. Pat. No. 6,093,856 allof which is incorporated herein by reference. These branched nonionicsurfactants show, some in applications, improved spotting and filmingbenefits over conventional linear surfactants.

Anionic Surfactant

Essentially any anionic surfactants useful for detersive purposes aresuitable. These can include salts (including, for example, sodium,potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of the anionic sulfate, sulfonate,carboxylate and sarcosinate surfactants. Anionic sulfate surfactants arepreferred.

Nonlimiting examples of surfactants useful herein include theconventional C₁₁-C₁₈ linear or branched alkyl benzene sulfonates andprimary, secondary, linear, branched and random alkyl sulfates, theC₁₀-C₁₈ alkyl alkoxy sulfates, the C₁₀-C₁₈ alkyl polyglycosides andtheir corresponding sulfated polyglycosides, C₁₂-C₁₈ alpha-sulfonatedfatty acid esters, C₁₂-C₁₈ alkyl and alkyl phenol alkoxylates(especially ethoxylates and mixed ethoxy/propoxy), C₁₂-C₁₈ betaines andsulfobetaines (“sultaines”), C₁₀-C₁₈ amine oxides, and the like. Otherconventional usefuil surfactants are listed in standard texts. Otheranionic surfactants include the isethionates such as the acylisethionates, N-acyl taurates, fatty acid amides of methyl tauride,alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate(especially saturated and unsaturated C₁₂-C₁₈ monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C₆-C₁₄ diesters),N-acyl sarcosinates. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tallow oil.

Especially suitable surfactants are the mid-chain branched surfactants.These include, mid-chain branched alkyl sulfates, mid-chain branchedalkyl alkoxy sulfates and mid-chain branched alkyl alkoxylates. Thereare two types of especially preferred branched surfactants they are thesasol type and the shell type. The sasol type surfactants are asurfactant system comprising a branched surfactant mixture, saidbranched surfactant mixture comprising mid-chain branched and linearsurfactant compounds, said linear compounds exceeding at least about 25%and less than about 70%, by weight of the branched surfactant mixturewherein the mid-chain branched surfactant compounds are of the formula:

A ^(b) −B

wherein A^(b) is a hydrophobic moiety having from about 10 to about 18total carbons divided between a longest chain and at least one shortchain, the longest chain being in the range of from about 9 to about 17carbon atoms, there being one or more C₁-C₃ alkyl moieties branchingfrom the longest chain, provided that at least one of the branchingalkyl moieties is attached directly to a carbon of the longest linearcarbon chain at a position within the range of position 3 carbon,counting from carbon #1 which is attached to the—B moiety, to positionω—2 carbon, wherein ω is the terminal carbon B is a hydrophilic moietyselected from the group consisting of OSO₃M, (EO/PO), (EO/PO)mOSO₃M andmixtures thereof, wherein EO/PO are alkoxy moieties selected from thegroup consisting of ethoxy, propoxy, and mixtures thereof, wherein m isat least about 1 to about 30 and M is hydrogen or a salt forming cationprovided that the average total number of carbon atoms in the A^(b)moiety in the branched surfactant mixture is within the range of greaterthan about 11 to about 14.5.

The shell type surfactants surfactant system comprising a branchedsurfactant mixture, said branched surfactant mixture comprisingmid-chain branched and linear surfactant compounds, said linearcompounds less than about 25% by weight of the branched surfactantmixture wherein the mid-chain branched surfactant compounds are of theformula:

A ^(b) −B

wherein A^(b) is a hydrophobic moiety having from about 10 to about 18total carbons divided between a longest chain and at least one shortchain, the longest chain being in the range of from about 9 to about 17carbon atoms, there being one or more C₁-C₃ alkyl moieties branchingfrom the longest chain, provided that at least one of the branchingalkyl moieties is attached directly to a carbon of the longest linearcarbon chain at a position within the range of position 3 carbon,counting from carbon #1 which is attached to the—B moiety, to positionω—2 carbon, wherein ω is the terminal carbon B is a hydrophilic moietyselected from the group consisting of OSO₃M, (EO/PO), (EO/PO)mOSO₃M andmixtures thereof, wherein EO/PO are alkoxy moieties selected from thegroup consisting of ethoxy, propoxy, and mixtures thereof, wherein m isat least about 1 to about 30 and M is hydrogen or a salt forming cationprovided that the average total number of carbon atoms in the A^(b)moiety in the branched surfactant mixture is within the range of greaterthan about 11 to about 14.5.

See U.S. patent applications Ser. Nos. 60/061,971 filed Oct. 14, 1997,U.S. Ser. No. 60/061,975 filed Oct. 14, 1997, 60/062,086 filed Oct. 14,1997, U.S. Ser. No. 60/061,916 filed Oct. 14, 1997, U.S. Ser. No.60/061,970 filed Oct. 14, 1997 and U.S. Ser. No. 60/062,407 filed Oct.14, 1997 all of which are incorporated herein by reference. Othermid-chain branched surfactants can be found in U.S. patent applicationsSer. Nos. 60/031,845 and 60/031,916 which continued as U.S. applicationSer. No. 09/170167, now U.S. Pat. No. 6,020,303.

Anionic sulfate surfactants suitable for use herein include the linearand branched primary and secondary alkyl sulfates, alkyl ethoxysulfates,fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ethersulfates, the C₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl)glucamine sulfates, and sulfates of alkylpolysaccharides such as thesulfates of alkylpolyglucoside (the nonionic nonsulfated compounds beingdescribed herein).

Alkyl sulfate surfactants are preferably selected from the linear andbranched primary C₁₀-C₁₈ alkyl sulfates, more preferably the C₁₁-C₁₅branched chain alkyl sulfates and the C₁₂-C₁₄ linear chain alkylsulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the groupconsisting of the C₁₀-C₁₈ alkyl sulfates which have been ethoxylatedwith from 0.5 to 20 moles of ethylene oxide per molecule. Morepreferably, the alkyl ethoxysulfate surfactant is a C₁₁-C₁₈, mostpreferably C₁₁-C₁₅ alkyl sulfate which has been ethoxylated with from0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of thepreferred alkyl sulfate and alkyl ethoxysulfate surfactants. Suchmixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic sulfonate surfactants suitable for use herein include the saltsof C₅-C₂₀ linear or branched alkylbenzene sulfonates, alkyl estersulfonates, C₆-C₂₂ primary or secondary alkane sulfonates, C₆-C₂₄ olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates,fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and anymixtures thereof.

Suitable anionic carboxylate surfactants include the alkyl ethoxycarboxylates, the alkyl polyethoxy polycarboxylate surfactants and thesoaps (‘alkyl carboxyls’), especially certain secondary soaps asdescribed herein.

Suitable alkyl ethoxy carboxylates include those with the formulaRO(CH₂CH₂O)_(x) CH₂COO⁻M⁺wherein R is a C₆ to C₁₈ alkyl group, x rangesfrom 0 to 10, and the ethoxylate distribution is such that, on a weightbasis, the amount of material where x is 0 is less than 20% and M is acation. Suitable alkyl polyethoxy polycarboxylate surfactants includethose having the formula RO—(CHR₁—CHR₂—O)—R₃ wherein R is a C₆ to C₁₈alkyl group, x is from 1 to 25, R₁ and R₂ are selected from the groupconsisting of hydrogen, methyl acid radical, succinic acid radical,hydroxysuccinic acid radical, and mixtures thereof, and R₃ is selectedfrom the group consisting of hydrogen, substituted or unsubstitutedhydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants whichcontain a carboxyl unit connected to a secondary carbon. Preferredsecondary soap surfactants for use herein are water-soluble membersselected from the group consisting of the water-soluble salts of2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-l-nonanoicacid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certainsoaps may also be included as suds suppressors.

Other suitable anionic surfactants are the alkali metal sarcosinates offormula R—CON (R¹) CH₂ COOM, wherein R is a C₅-C₁₇ linear or branchedalkyl or alkenyl group, R¹ is a C₁-C₄ alkyl group and M is an alkalimetal ion. Preferred examples are the myristyl and oleoyl methylsarcosinates in the form of their sodium salts.

Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formulaR³(OR⁴)_(x)N⁰(R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl,acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containingfrom 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene groupcontaining from 2 to 3 carbon atoms, or mixtures thereof, x is from 0 to5, preferably from 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl groupcontaining from 1 to 3, or a polyethylene oxide group containing from 1to 3 ethylene oxide groups. Preferred are C₁₀-C₁₈ alkyl dimethylamineoxide, and C₁₀-C₁₈ acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(™) C2MConc. manufactured by Miranol, Inc., Dayton, N.J.

Zwitterionic Surfactant

Zwitterionic surfactants can also be incorporated into the detergentcompositions hereof. These surfactants can be broadly described asderivatives of secondary and tertiary amines, derivatives ofheterocyclic secondary and tertiary amines, or derivatives of quaternaryammonium, quaternary phosphonium or tertiary sulfonium compounds.Betaine and sultaine surfactants are exemplary zwitterionic surfactantsfor use herein.

Suitable betaines are those compounds having the formula R(R′)₂N+R²COO—wherein R is a C₆-C₁₈ hydrocarbyl group, each R¹ is typically C₁-C₃alkyl, and R² is a C₁-C₅ hydrocarbyl group. Preferred betaines areC₁₂-C₁₈ dimethyl-ammonio hexanoate and the C₁₀-C₁₈ acylamidopropane (orethane) dimethyl (or diethyl) betaines. Complex betaine surfactants arealso suitable for use herein.

Cationic Surfactants

Cationic ester surfactants used in this invention are preferably waterdispersible compound having surfactant properties comprising at leastone ester (i.e. —COO—) linkage and at least one cationically chargedgroup. Other suitable cationic ester surfactants, including cholineester surfactants, have for example been disclosed in U.S. Pat. Nos.4228042, 4239660 and 4260529.

Suitable cationic surfactants include the quaternary ammoniumsurfactants selected from mono C₆-C₁₆, preferably C₆-C₁₀ N-alkyl oralkenyl ammonium surfactants wherein the remaining N positions aresubstituted by methyl, hydroxyethyl or hydroxypropyl groups.

Detergent Builders

The present invention may include an optional builder in the productcomposition. The level of detergent salt/builder can vary widelydepending upon the end use of the composition and its desired physicalform. When present, the compositions will typically, comprise at leastabout 1% detergent builder and more typically from about 10% to about80%, even more typically from about 15% to about 50% by weight, of thedetergent builder. Lower or higher levels, however, are not meant to beexcluded.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate salts arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called “weak” builders(as compared with phosphates) such as citrate, or in the so-called“underbuilt” situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂:Na₂O ratio in the range 1.6:1 to 3.2:1and layered silicates, such as the layered sodium silicates described inU.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 isthe trademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as “SKS-6”). Unlike zeolite builders, theNa SKS-6 silicate builder does not contain aluminum. NaSKS-6 has thedelta-Na₂SiO₅ morphology form of layered silicate. It can be prepared bymethods such as those described in German DE-A-3,417,649 andDE-A-3,742,043. SKS-6 is a highly preferred layered silicate for useherein, but other such layered silicates, such as those having thegeneral formula NaMSi_(x)O_(2x+1).yH₂O wherein M is sodium or hydrogen,x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to20, preferably 0 can be used herein. Various other layered silicatesfrom Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, betaand gamma forms. As noted above, the delta-Na₂SiO₅ (NaSKS-6 form) ismost preferred for use herein. Other silicates may also be useful suchas for example magnesium silicate, which can serve as a crispening agentin granular formulations, as a stabilizing agent for oxygen bleaches,and as a component of suds control systems.

Examples of carbonate salts as builders are the alkaline earth andalkali metal carbonates as disclosed in German Patent Application No.2,321,001 published on Nov. 15, 1973.

Aluminosilicate builders may also be added to the present invention as adetergent salt. Aluminosilicate builders are of great importance in mostcurrently marketed heavy duty granular detergent compositions.Aluminosilicate builders include those having the empirical formula:

M_(z)[(SiO₂)_(w)(AlO₂)_(y)].xH₂O

wherein z, w and y are integers of at least 6, the molar ratios of z toy and z to w are in the range from 1.0 to about 0.5, and x is an integerfrom about 15 to about 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0−10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, “polycarboxylate” refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also“TMS/TDS” builders of U.S. Pat. No. 4,663,071, issued to Bush et al, onMay 5, 1987. Suitable ether polycarboxylates also include cycliccompounds, particularly alicyclic compounds, such as those described inU.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonicacid, and carboxymethyloxysuccinic acid, the various alkali metal,ammonium and substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance. Oxydisuccinates are also especially usefuil in suchcompositions and combinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅-C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

Bleaching Agents

Bleaching agents according to the present invention may include bothchlorine and oxygen bleaching systems. Hydrogen peroxide sources aredescribed in detail in the herein incorporated Kirk Othmer'sEncyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons),Vol. 4, pp. 271-300 “Bleaching Agents (Survey)”, and include the variousforms of sodium perborate and sodium percarbonate, including variouscoated and modified forms. An “effective amount” of a source of hydrogenperoxide is any amount capable of measurably improving stain removal(especially of tea stains) from soiled dishware compared to a hydrogenperoxide source-free composition when the soiled dishware is washed bythe consumer in a domestic automatic dishwasher in the presence ofalkali.

More generally a source of hydrogen peroxide herein is any convenientcompound or mixture which under consumer use conditions provides aneffective amount of hydrogen peroxide. Levels may vary widely and areusually in the range from about 0.1% to about 70%, more typically fromabout 0.5% to about 30%, by weight of the compositions herein.

The preferred source of hydrogen peroxide used herein can be anyconvenient source, including hydrogen peroxide itself. For example,perborate, e.g., sodium perborate (any hydrate but preferably the mono-or tetra-hydrate), sodium carbonate peroxyhydrate or equivalentpercarbonate salts, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, or sodium peroxide can be used herein. Also useful aresources of available oxygen such as persulfate bleach (e.g., OXONE,manufactured by DuPont). Sodium perborate monohydrate and sodiumpercarbonate are particularly preferred. Mixtures of any convenienthydrogen peroxide sources can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with a silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

While not preferred for compositions of the present invention whichcomprise detersive enzymes, the present invention compositions may alsocomprise as the bleaching agent a chlorine-type bleaching material. Suchagents are well known in the art, and include for example sodiumdichloroisocyanurate (“NaDCC”), or sodium hypochlorite (NaOCl).

(a) Bleach Activators

Preferably, the peroxygen bleach component in the composition isformulated with an activator (peracid precursor). The activator ispresent at levels of from about 0.01% to about 15%, preferably fromabout 0.5% to about 10%, more preferably from about 1% to about 8%, byweight of the composition. Preferred activators are selected from thegroup consisting of tetraacetyl ethylene diamine (TAED),benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam,3-chlorobenzoyl-caprolactam, benzoyloxybenzenesulphonate (BOBS),nonanoyloxybenzene-sulphonate (NOBS), phenyl benzoate (PhiBz),decanoyloxybenzenesulphonate (C₁₀-OBS), benzoylvalerolactam (BZVL),octanoyloxybenzenesulphonate (C₈-OBS), perhydrolyzable esters andmixtures thereof, most preferably benzoylcaprolactam andbenzoylvalerolactam. Particularly preferred bleach activators in the pHrange from about 8 to about 9.5 are those selected having an OBS or VLleaving group.

Preferred bleach activators are those described in U.S. Pat. No.5,130,045, Mitchell et al, and U.S. Pat. No. 4,412,934, Chung et al, andpatent applications U.S. Ser. Nos. 08/064,624, 08/064,623, 08/064,621,08/064,562, 08/064,564, all abandoned and application to M. Bums, A. D.Willey, R. T. Hartshom, C. K. Ghosh, entitled “Bleaching CompoundsComprising Peroxyacid Activators Used With Enzymes” and having U.S. Ser.No. 08/133,691 (P&G Case 4890R)now abandoned, all of which areincorporated herein by reference.

The mole ratio of peroxygen bleaching compound (as AvO) to bleachactivator in the present invention generally ranges from at least 1:1,preferably from about 20:1 to about 1:1, more preferably from about 10:1to about 3:1.

Quatemary substituted bleach activators may also be included. Thepresent detergent compositions preferably comprise a quaternarysubstituted bleach activator (QSBA) or a quatemary substituted peracid(QSP); more preferably, the former. Preferred QSBA structures arefurther described in U.S. Pat. Nos. 5,460,747, 5,584,888 and 5,578,136,incorporated herein by reference.

(b) Organic Peroxides, Especially Diacyl Peroxides

These are extensively illustrated in Kirk Othmer, Encyclopedia ofChemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90and especially at pages 63-72, all incorporated herein by reference. Ifa diacyl peroxide is used, it will preferably be one which exertsminimal adverse impact on spotting/filming. Preferred is dibenzoylperoxide.

(c) Metal-containing Bleach Catalysts

The present invention compositions and methods utilize metal-containingbleach catalysts that are effective for use in ADD compositions.Preferred are manganese and cobalt-containing bleach catalysts.

One type of metal-containing bleach catalyst is a catalyst systemcomprising a transition metal cation of defined bleach catalyticactivity, such as copper, iron, titanium, ruthenium tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexesdisclosed in U.S. Pat. No. 5,246,621 and U.S. Pat. No. 5,244,594.Preferred examples of theses catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(PF₆)₂ (“MnTACN”),Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄-(ClO₄)₂, Mn^(III)Mn^(IV)_(4(u-O)) ₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₃,and mixtures thereof. See also European patent application publicationno. 549,272. Other ligands suitable for use herein include1,5,9-trimethyl-1,5,9-triazacyclododecane,2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, andmixtures thereof.

The bleach catalysts useful in automatic dishwashing compositions andconcentrated powder detergent compositions may also be selected asappropriate for the present invention. For examples of suitable bleachcatalysts see U.S. Pat. No. 4,246,612 and U.S. Pat. No. 5,227,084.

Other bleach catalysts are described, for example, in European patentapplication, publication no. 408,131 (cobalt complex catalysts),European patent applications, publication nos. 384,503, and 306,089(metallo-porphyrin catalysts), U.S. Pat. No. 4,728,455(manganese/multidentate ligand catalyst), U.S. Pat. No. 4,711,748 andEuropean patent application, publication no. 224,952, (absorbedmanganese on aluminosilicate catalyst), U.S. Pat. No. 4,601,845(aluminosilicate support with manganese and zinc or magnesium salt),U.S. Pat. No. 4,626,373 (manganese/ligand catalyst), U.S. Pat. No.4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019(cobalt chelant catalyst) Canadian 866,191 (transition metal-containingsalts), U.S. Pat. No. 4,430,243 (chelants with manganese cations andnon-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganesegluconate catalysts).

Preferred are cobalt catalysts which have the formula:

[Co(NH₃)_(n)(M′)_(m)]Y_(y)

wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably5); M′ is a labile coordinating moiety, preferably selected from thegroup consisting of chlorine, bromine, hydroxide, water, and (when m isgreater than 1) combinations thereof; m is an integer from 1 to 3(preferably 1 or 2; most preferably 1); m+n=6; and Y is an appropriatelyselected counteranion present in a number y, which is an integer from 1to 3 (preferably 2 to 3; most preferably 2 when Y is a −1 chargedanion), to obtain a charge-balanced salt.

The preferred cobalt catalyst of this type useful herein are cobaltpentaamine chloride salts having the formula [Co(NH₃)₅Cl] Y_(y), andespecially [Co(NH₃)₅Cl]Cl₂.

More preferred are the present invention compositions which utilizecobalt (III) bleach catalysts having the formula:

[Co(NH₃)_(n)(M)_(m)(B)_(b)]T_(y)

wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5);M is one or more ligands coordinated to the cobalt by one site; m is 0,1 or 2 (preferably 1); B is a ligand coordinated to the cobalt by twosites; b is 0 or 1 (preferably 0), and when b=0, then m+n=6, and whenb=1, then m=0 and n=4; and T is one or more appropriately selectedcounteranions present in a number y, where y is an integer to obtain acharge-balanced salt (preferably y is 1 to 3; most preferably 2 when Tis a −1 charged anion); and wherein further said catalyst has a basehydrolysis rate constant of less than 0.23 M⁻¹ s⁻¹ (25° C.).

Preferred T are selected from the group consisting of chloride, iodide,I₃ ⁻, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate,carbonate, bromide, PF₆ ⁻, BF₄ ⁻, B(Ph)₄ ⁻, phosphate, phosphite,silicate, tosylate, methanesulfonate, and combinations thereof.Optionally, T can be protonated if more than one anionic group exists inT, e.g., HPO₄ ²⁻, HCO³⁻, H₂PO⁴⁻, etc. Further, T may be selected fromthe group consisting of non-traditional inorganic anions such as anionicsurfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates(AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g.,polyacrylates, polymethacrylates, etc.).

The M moieties include, but are not limited to, for example, F⁻, SO₄ ⁻²,NCS⁻, SCN⁻, S₂O₃ ⁻², NH₃, PO₄ ³⁻, and carboxylates (which preferably aremono-carboxylates, but more than one carboxylate may be present in themoiety as long as the binding to the cobalt is by only one carboxylateper moiety, in which case the other carboxylate in the M moiety may beprotonated or in its salt form). Optionally, M can be protonated if morethan one anionic group exists in M (e.g., HPO₄ ²⁻, HCO₃ ⁻, H₂PO⁴⁻,HOC(O)CH₂C(O)O—, etc.) Preferred M moieties are substituted andunsubstituted C₁-C₃₀ carboxylic acids having the formulas:

RC(O)O—

wherein R is preferably selected from the group consisting of hydrogenand C₁-C₃₀ (preferably C₁-C₁₈) unsubstituted and substituted alkyl,C₆-C₃₀ (preferably C₆-C₁₈) unsubstituted and substituted aryl, andC₃-C₃₀ (preferably C₅-C₁₈) unsubstituted and substituted heteroaryl,wherein substituents are selected from the group consisting of —NR′₃,—NR′₄ ⁺, —C(O)OR′, —OR′, —C(O)NR′₂, wherein R′ is selected from thegroup consisting of hydrogen and C₁-C₆ moieties. Such substituted Rtherefore include the moieties —(CH₂)_(n)OH and —(CH₂)_(n)NR′₄ ⁺,wherein n is an integer from 1 to about 16, preferably from about 2 toabout 10, and most preferably from about 2 to about 5.

Most preferred M are carboxylic acids having the formula above wherein Ris selected from the group consisting of hydrogen, methyl, ethyl,propyl, straight or branched C₄-C₁₂ alkyl, and benzyl. Most preferred Ris methyl. Preferred carboxylic acid M moieties include formic, benzoic,octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic,adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic,triflate, tartrate, stearic, butyric, citric, acrylic, aspartic,fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.

The B moieties include carbonate, di- and higher carboxylates (e.g.,oxalate, malonate, malic, succinate, maleate), picolinic acid, and alphaand beta amino acids (e.g., glycine, alanine, beta-alanine,phenylalanine).

Cobalt bleach catalysts useful herein are known, being described forexample along with their base hydrolysis rates, in M. L. Tobe, “BaseHydrolysis of Transition-Metal Complexes”, Adv. Inorg. Bioinorg. Mech.,(1983), 2, pages 1-94. For example, Table 1 at page 17, provides thebase hydrolysis rates (designated therein as kOH) for cobalt pentaaminecatalysts complexed with oxalate (k_(OH)=2.5×10⁻⁴ M⁻¹ s⁻¹ (25° C.)),NCS⁻(k_(OH)=5.0×10⁻⁴ M⁻¹ s⁻¹ (25° C.)), formate (k_(OH)=5.8×10⁻⁴ M⁻¹ s⁻¹(25° C.)), and acetate (k_(OH)=9.6×10⁻⁴ M⁻¹ s⁻¹ (25° C.)). The mostpreferred cobalt catalyst useful herein are cobalt pentaamine acetatesalts having the formula [Co(NH₃)₅OAc] T_(y), wherein OAc represents anacetate moiety, and especially cobalt pentaamine acetate chloride,[Co(NH₃)₅OAc]Cl₂; as well as [Co(NH₃)₅OAc](OAc)₂; [Co(NH₃)₅OAc](PF₆)₂;[Co(NH₃)₅OAc](SO₄); [Co(NH₃)₅OAc](BF₄)₂; and [Co(NH₃)₅OAc](NO₃)₂.

Cobalt catalysts according to the present invention made be producedaccording to the synthetic routes disclosed in U.S. Pat. Nos. 5,559,261,5,581,005, and 5,597,936, the disclosures of which are hereinincorporated by reference.

These catalysts may be co-processed with adjunct materials so as toreduce the color impact if desired for the aesthetics of the product, orto be included in enzyme-containing particles as exemplifiedhereinafter, or the compositions may be manufactured to contain catalyst“speckles”.

As a practical matter, and not by way of limitation, the cleaningcompositions and cleaning processes herein can be adjusted to provide onthe order of at least one part per hundred million of the active bleachcatalyst species in the aqueous washing medium, and will preferablyprovide from about 0.01 ppm to about 25 ppm, more preferably from about0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm toabout 5 ppm, of the bleach catalyst species in the wash liquor. In orderto obtain such levels in the wash liquor of an automatic dishwashingprocess, typical automatic dishwashing compositions herein will comprisefrom about 0.0005% to about 0.2%, more preferably from about 0.004% toabout 0.08%, of bleach catalyst by weight of the cleaning compositions.

Controlled Rate of Release

The detergent tablet may be provided with a way for controlling the rateof release of bleaching agent, particularly oxygen bleach to the washsolution.

The controlling of the rate of release of the bleach may provide forcontrolled release of peroxide species to the wash solution. This could,for example, include controlling the release of any inorganic perhydratesalt, acting as a hydrogen peroxide source, to the wash solution.

Suitable ways of controlled release of the bleaching agent can includeconfining the bleach to either the compressed or non-compressed,non-encapsulating portions. Where more than one non-compressed,non-encapsulating portions are present, the bleach may be confined tothe first and/or second and/or optional subsequent non-compressed,non-encapsulating portions.

Another way for controlling the rate of release of bleach may be bycoating the bleach with a coating designed to provide the controlledrelease. The coating may therefore, for example, comprise a poorly watersoluble material, or be a coating of sufficient thickness that thekinetics of dissolution of the thick coating provide the controlled rateof release.

The coating material may be applied using various methods. Any coatingmaterial is typically present at a weight ratio of coating material tobleach of from 1:99 to 1:2, preferably from 1:49 to 1:9.

Suitable coating materials include triglycerides (e.g. partially)hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono ordiglycerides, microcrystalline waxes, gelatin, cellulose, fatty acidsand any mixtures thereof.

Other suitable coating materials can comprise the alkali and alkalineearth metal sulphates, silicates and carbonates, including calciumcarbonate and silicas.

A preferred coating material, particularly for an inorganic perhydratesalt bleach source, comprises sodium silicate of SiO₂:Na₂O ratio fromabout 1.8:1 to about 3.0:1, preferably about 1.8:1 to about 2.4:1,and/or sodium metasilicate, preferably applied at a level of from about2% to about 10%, (normally from about 3% to about 5%) of SiO₂ by weightof the inorganic perhydrate salt. Magnesium silicate can also beincluded in the coating.

Any inorganic salt coating materials may be combined with organic bindermaterials to provide composite inorganic salt/organic binder coatings.Suitable binders include the C₁₀-C₂₀ alcohol ethoxylates containing from5-100 moles of ethylene oxide per mole of alcohol and more preferablythe C₁₅-C₂₀ primary alcohol ethoxylates containing from 20-100 moles ofethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials.Polyvinylpyrrolidones with an average molecular weight of from 12,000 to700,000 and polyethylene glycols (PEG) with an average molecular weightof from 600 to 5×10⁶ preferably 1000 to 400,000 most preferably 1000 to10,000 are examples of such polymeric materials. Copolymers of maleicanhydride with ethylene, methylvinyl ether or methacrylic acid, themaleic anhydride constituting at least 20 mole percent of the polymerare further examples of polymeric materials useful as binder agents.These polymeric materials may be used as such or in combination withsolvents such as water, propylene glycol and the above mentioned C₁₀-C₂₀alcohol ethoxylates containing from 5-100 moles of ethylene oxide permole. Further examples of binders include the C₁₀-C₂₀ mono- anddiglycerol ethers and also the C₁₀-C₂₀ fatty acids.

Cellulose derivatives such as methylcellulose, carboxymethylcelluloseand hydroxyethylcellulose, and homo- or co-polymeric polycarboxylicacids or their salts are other examples of binders suitable for useherein.

One method for applying the coating material involves agglomeration.Preferred agglomeration processes include the use of any of the organicbinder materials described hereinabove. Any conventionalagglomerator/mixer may be used including, but not limited to pan, rotarydrum and vertical blender types. Molten coating compositions may also beapplied either by being poured onto, or spray atomized onto a moving bedof bleaching agent.

Other ways of providing the required controlled release include alteringthe physical characteristics of the bleach to control its solubility andrate of release. Suitable ways could include compression, mechanicalinjection, manual injection, and adjustment of the solubility of thebleach compound by selection of particle size of any particulatecomponent.

Whilst the choice of particle size will depend both on the compositionof the particulate component, and the desire to meet the desiredcontrolled release kinetics, it is desirable that the particle sizeshould be more than 500 micrometers, preferably having an averageparticle diameter of from 800 to 1200 micrometers.

Additional ways for providing controlled release include the suitablechoice of any other components of the detergent composition matrix suchthat when the composition is introduced to the wash solution the ionicstrength environment therein provided enables the required controlledrelease kinetics to be achieved.

Detersive Enzymes

The compositions of the present invention may also include the presenceof at least one detersive enzyme. “Detersive enzyme”, as used herein,means any enzyme having a cleaning, stain removing or otherwisebeneficial effect in a composition. Preferred detersive enzymes arehydrolases such as proteases, amylases and lipases. Highly preferred forautomatic dishwashing are amylases and/or proteases, including bothcurrent commercially available types and improved types which, thoughmore bleach compatible, have a remaining degree of bleach deactivationsusceptibility.

In general, as noted, preferred compositions herein comprise one or moredetersive enzymes. If only one enzyme is used, it is preferably anamyolytic enzyme when the composition is for automatic dishwashing use.Highly preferred for automatic dishwashing is a mixture of proteolyticenzymes and amyloytic enzymes. More generally, the enzymes to beincorporated include proteases, amylases, lipases, cellulases, andperoxidases, as well as mixtures thereof. Other types of enzymes mayalso be included. They may be of any suitable origin, such as vegetable,animal, bacterial, fungal and yeast origin. However, their choice isgoverned by several factors such as pH-activity and/or stability optima,thermostability, stability versus active detergents, builders, etc. Inthis respect bacterial or fungal enzymes are preferred, such asbacterial amylases and proteases, and fungal cellulases.

Enzymes are normally incorporated in the instant detergent compositionsat levels sufficient to provide a “cleaning-effective amount”. The term“cleaning-effective amount” refers to any amount capable of producing acleaning, stain removal or soil removal effect on substrates such asfabrics, dishware and the like. Since enzymes are catalytic materials,such amounts may be very small. In practical terms for currentcommercial preparations, typical amounts are up to about 5 mg by weight,more typically about 0.01 mg to about 3 mg, of active enzyme per gram ofthe composition. Stated otherwise, the compositions herein willtypically comprise from about 0.001% to about 6%, preferably about 0.01%to about 1% by weight of a commercial enzyme preparation. Proteaseenzymes are usually present in such commercial preparations at levelssufficient to provide from 0.005 to 0.1 Anson units (AU) of activity pergram of composition. For automatic dishwashing purposes, it may bedesirable to increase the active enzyme content of the commercialpreparations, in order to minimize the total amount of non-catalyticallyactive materials delivered and thereby improve spotting/filming results.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Anothersuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold by NovoIndustries A/S as ESPERASE®. The preparation of this enzyme andanalogous enzymes is described in British Patent Specification No.1,243,784 of Novo. Proteolytic enzymes suitable for removingprotein-based stains that are commercially available include those soldunder the tradenames ALCALASE® and SAVINASE® by Novo Industries A/S(Denmark) and MAXATASE® by International Bio-Synthetics, Inc. (TheNetherlands) and PURAFECT®, by GCI. Other proteases include Protease A(see European Patent Application 130,756, published Jan. 9, 1985) andProtease B (see European Patent Application Serial No. 87303761.8, filedApr. 28, 1987, now EP 251446 and European Patent Application 130,756,Bott et al, published Jan. 9, 1985).

An especially preferred protease, referred to as “Protease D” is acarbonyl hydrolase variant having an amino acid sequence not found innature, which is derived from a precursor carbonyl hydrolase bysubstituting a different amino acid for a plurality of amino acidresidues at a position in said carbonyl hydrolase equivalent to position+76, preferably also in combination with one or more amino acid residuepositions equivalent to those selected from the group consisting of +99,+101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156,+166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265,and/or +274 according to the numbering of Bacillus amyloliquefacienssubtilisin, as described in WO 95/10615 published Apr. 20, 1995 byGenencor International.

Other preferred protease enzymes include protease enzymes which are acarbonyl hydrolase variant having an amino acid sequence not found innature, which is derived by replacement of a plurality of amino acidresidues of a precursor carbonyl hydrolase with different amino acids,wherein said plurality of amino acid residues replaced in the precursorenzyme correspond to position +210 in combination with one or more ofthe following residues: +33, +62, +67, +76, +100, +101, +103, +104,+107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170,+209, +215, +217, +218 and +222, where the numbered positions correspondto naturally-occurring subtilisin from Bacillus amyloliquefaciens or toequivalent amino acid residues in other carbonyl hydrolases orsubtilisins (such as Bacillus lentus subtilisin). Preferred enzymesaccording include those having position changes +210, +76, +103, +104,+156, and +166.

Useful proteases are also described in PCT publications: WO 95/30010published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/30011published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/29979published Nov. 9, 1995 by The Procter & Gamble Company.

Amylases suitable herein include, for example, α-amylases described inBritish Patent Specification No. 1,296,839 (Novo), RAPIDASE®,International Bio-Synthetics, Inc. ENDOLASE, by Novo Industries andTERMAMYL®, Novo Industries.

Preferred amylases herein have the commonalty of being derived usingsite-directed mutagenesis from one or more of the Baccillus amylases,especially the Bacillus alpha-amylases, regardless of whether one, twoor multiple amylase strains are the immediate precursors.

As noted, “oxidative stability-enhanced” amylases are preferred for useherein despite the fact that the invention makes them “optional butpreferred” materials rather than essential. Such amylases arenon-limitingly illustrated by the following:

(a) An amylase according to the hereinbefore incorporated WO/94/02597,Novo Nordisk A/S, published Feb. 3, 1994, as further illustrated by amutant in which substitution is made, using alanine or threonine(preferably threonine), of the methionine residue located in position197 of the B.licheniformis alpha-amylase, known as TERMAMYL®, or thehomologous position variation of a similar parent amylase, such as B.amyloliquefaciens, B. subtilis, or B. stearothermophilus;

(b) Stability-enhanced amylases as described by Genencor Internationalin a paper entitled “Oxidatively Resistant alpha-Amylases” presented atthe 207th American Chemical Society National Meeting, Mar. 13-17 1994,by C. Mitchinson. Therein it was noted that bleaches in automaticdishwashing detergents inactivate alpha-amylases but that improvedoxidative stability amylases have been made by Genencor fromB.licheniformis NCIB8061. Methionine (Met) was identified as the mostlikely residue to be modified. Met was substituted, one at a time, inpositions 8,15,197,256,304,366 and 438 leading to specific mutants,particularly important being M197L and M197T with the M197T variantbeing the most stable expressed variant. Stability was measured inCASCADE® and SUNLIGHT®;

(c) Also preferred herein are amylase variants having additionalmodification in the immediate parent available from Novo Nordisk A/S andare those referred to by the supplier under the tradename DURMAMYL®;

(d) Particularly preferred are amylase variants as disclosed inWO95/26397 and in the co-pending application to Novo NordiskPCT/DK96/00056 now WO 96/23893 and characterized by having a specificactivity at least 25% higher than the specific activity of Termamyl® ata temperature range of 25° C. to 55° C. and at a pH value in the rangeof 8 to 10, measured by the Phadebas® α-amylase activity assay and isobtained from an alkalophilic Bacillus species (such as the strains NC1B12289, NCIB 12512, NCIB 12513 and DSM 935) comprising the followingamino acid sequence in the N-terminal:His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.

Cellulases usable in, but not preferred, for the present inventioninclude both bacterial or fungal cellulases. Typically, they will have apH optimum of between 5 and 9.5. Suitable cellulases are disclosed inU.S. Pat. No. 4,435,307, Barbesgoard et al, issued Mar. 6, 1984, whichdiscloses fungal cellulase produced from Humicola insolens and Humicolastrain DSM1800 or a cellulase 212-producing fungus belonging to thegenus Aeromonas, and cellulase extracted from the hepatopancreas of amarine mollusk (Dolabella Auricula Solander). Suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.CAREZYME® (Novo) is especially useful.

Suitable lipase enzymes for detergent use include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent 1,372,034. See also lipasesin Japanese Patent Application 53,20487, laid open to public inspectionon Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co.Ltd., Nagoya, Japan, under the trade name Lipase P “Amano,” hereinafterreferred to as “Amano-P.” Other commercial lipases include Amano-CES,lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co.,Tagata, Japan; and further Chromobacter viscosum lipases from U.S.Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipasesex Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicolalanuginosa and commercially available from Novo (see also EPO 341,947)is a preferred lipase for use herein. Another preferred lipase enzyme isthe D96L variant of the native Humicola lanuginosa lipase, as describedin WO 92/05249 and Research Disclosure No. 35944, Mar. 10, 1994, bothpublished by Novo. In general, lipolytic enzymes are less preferred thanamylases and/or proteases for automatic dishwashing embodiments of thepresent invention.

Peroxidase enzymes can be used in combination with oxygen sources, e.g.,percarbonate, perborate, persulfate, hydrogen peroxide, etc. They aretypically used for “solution bleaching,” i.e. to prevent transfer ofdyes or pigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813, published Oct. 19, 1989,by O. Kirk, assigned to Novo Industries A/S. The present inventionencompasses peroxidase-free automatic dishwashing compositionembodiments.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent compositions are also disclosed in U.S. Pat. No.3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, issued Jul. 18, 1978,and in U.S. Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985. Enzymesfor use in detergents can be stabilized by various techniques. Enzymestabilization techniques are disclosed and exemplified in U.S. Pat. No.3,600,319, issued Aug. 17, 1971 to Gedge, et al, and European PatentApplication Publication No. 0 199 405, Application No. 86200586.5 now EP199405, published Oct. 29, 1986, Venegas. Enzyme stabilization systemsare also described, for example, in U.S. Pat. No. 3,519,570.

Disrupting Agents

As it was stated above, the detergent tablet of the present inventionmay further comprise a disrupting agent. Disrupting agents are typicallyincluded in the tablet at levels of from about 5% to about 60%, and morepreferably from about 20% to about 50%, by weight. The disrupting agentmay be a disintegrating or effervescing agent. Suitable disintegratingagents include agents that swell on contact with water or facilitatedwater influx and/or efflux by forming channels in compressed and/ornon-compressed portions. Any known disintegrating or effervescing agentsuitable for use in laundry or dishwashing applications is envisaged foruse herein. Suitable disintegrating agent include starch, starchderivatives, alginates, carboxymethylcellulose (CMC), cellulosic-basedpolymers, sodium acetate, aluminium oxide. Suitable effervescing agentsare those that produce a gas on contact with water. Suitableeffervescing agents may be oxygen, nitrogen dioxide or carbon dioxideevolving species. Examples of preferred effervescing agents may beselected from the group consisting of perborate, percarbonate,carbonate, bicarbonate and carboxylic acids such as citric or maleicacid.

pH and Buffering Variation

The detergent tablet compositions herein can be buffered, i.e., they arerelatively resistant to pH drop in the presence of acidic soils.However, other compositions herein may have exceptionally low bufferingcapacity, or may be substantially unbuffered. Techniques for controllingor varying pH at recommended usage levels more generally include the useof not only buffers, but also additional alkalis, acids, pH-jumpsystems, dual compartment containers, etc., and are well known to thoseskilled in the art.

The preferred compositions herein comprise a pH-adjusting componentselected from water-soluble alkaline inorganic salts and water-solubleorganic or inorganic builders. The pH-adjusting components are selectedso that when the composition is dissolved in water at a concentration of1,000-10,000 ppm, the pH remains in the range of above about 8,preferably from about 9.5 to about 11. The preferred nonphosphatepH-adjusting component of the invention is selected from the groupconsisting of:

(i) sodium carbonate or sesquicarbonate;

(ii) sodium silicate, preferably hydrous sodium silicate havingSiO₂:Na₂O ratio of from about 1:1 to about 2:1, and mixtures thereofwith limited quantities of sodium metasilicate;

(iii) sodium citrate;

(iv) citric acid;

(v) sodium bicarbonate;

(vi) sodium borate, preferably borax;

(vii) sodium hydroxide; and

(viii) mixtures of (i)-(vii).

Preferred embodiments contain low levels of silicate (i.e. from about 3%to about 10% SiO₂).

The amount of the pH adjusting component in the instant composition ispreferably from about 1% to about 50%, by weight of the composition. Ina preferred embodiment, the pH-adjusting component is present in thecomposition in an amount from about 5% to about 40%, preferably fromabout 10% to about 30%, by weight.

Water-Soluble Silicates

The present compositions may further comprise water-soluble silicates.Water-soluble silicates herein are any silicates which are soluble tothe extent that they do not adversely affect spotting/filmingcharacteristics of the ADD composition.

Examples of silicates are sodium metasilicate and, more generally, thealkali metal silicates, particularly those having a SiO₂:Na₂O ratio inthe range 1.6:1 to 3.2:1, preferably having a SiO₂:Na₂O ratio of about1.0 to about 3.0; and layered silicates, such as the layered sodiumsilicates described in U.S. Pat. No. 4,664,839, issued May 12, 1987 toH. P. Rieck. NaSKS-6® is a crystalline layered silicate marketed byHoechst (commonly abbreviated herein as “SKS-6”). Unlike zeolitebuilders, Na SKS-6 and other water-soluble silicates useful herein donot contain aluminum. NaSKS-6 is the δ-Na₂SiO₅ form of layered silicateand can be prepared by methods such as those described in GermanDE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a preferred layered silicatefor use herein, but other such layered silicates, such as those havingthe general formula NaMSi_(x)O_(2x+1).yH₂O wherein M is sodium orhydrogen, x is a number from 1.9 to 4, preferably 2, and y is a numberfrom 0 to 20, preferably 0 can be used. Various other layered silicatesfrom Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the α, β- andγ-forms. Other silicates may also be useful, such as for examplemagnesium silicate, which can serve as a crispening agent in granularformulations, as a stabilizing agent for oxygen bleaches, and as acomponent of suds control systems.

Silicates particularly useful in automatic dishwashing (ADD)applications include granular hydrous 2-ratio silicates such asBRITESIL® H20 from PQ Corp., and the commonly sourced BRITESIL® H24though liquid grades of various silicates can be used when the ADDcomposition has liquid form. Within safe limits, sodium metasilicate orsodium hydroxide alone or in combination with other silicates may beused in an ADD context to boost wash pH to a desired level.

Chelating Agents

The compositions herein may also optionally contain one or moretransition-metal selective sequestrants, “chelants” or “chelatingagents”, e.g., iron and/or copper and/or manganese chelating agents.Chelating agents suitable for use herein can be selected from the groupconsisting of aminocarboxylates, phosphonates (especially theaminophosphonates), polyfunctionally-substituted aromatic chelatingagents, and mixtures thereof. Without intending to be bound by theory,it is believed that the benefit of these materials is due in part totheir exceptional ability to control iron, copper and manganese inwashing solutions which are known to decompose hydrogen peroxide and/orbleach activators; other benefits include inorganic film prevention orscale inhibition. Commercial chelating agents for use herein include theDEQUEST® series, and chelants from Monsanto, DuPont, and Nalco, Inc.

Aminocarboxylates useful as optional chelating agents are furtherillustrated by ethylenediaminetetracetates,N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates,ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal,ammonium, and substituted ammonium salts thereof. In general, chelantmixtures may be used for a combination of functions, such as multipletransition-metal control, long-term product stabilization, and/orcontrol of precipitated transition metal oxides and/or hydroxides.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A highly preferred biodegradable chelator for use herein isethylenediamine disuccinate (“EDDS”), especially (but not limited to)the [S,S] isomer as described in U.S. Pat. No. 4,704,233, Nov. 3, 1987,to Hartman and Perkins. The trisodium salt is preferred though otherforms, such as magnesium salts, may also be useful.

Aminophosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorus are acceptable in detergent compositions, and include theethylenediaminetetrakis (methylenephosphonates) and thediethylenetriaminepentakis (methylene phosphonates). Preferably, theseaminophosphonates do not contain alkyl or alkenyl groups with more thanabout 6 carbon atoms.

If utilized, chelating agents or transition-metal-selective sequestrantswill preferably comprise from about 0.001% to about 10%, more preferablyfrom about 0.05% to about 1% by weight of the compositions herein.

Crystal Growth Inhibitor Component

The detergent tablets may preferably contain a crystal growth inhibitorcomponent, preferably an organodiphosphonic acid component, incorporatedmore preferably at a level of from about 0.01% to about 5%, even morepreferably from about 0.1% to about 2% by weight of the compositions.

By organo diphosphonic acid it is meant herein an organo diphosphonicacid which does not contain nitrogen as part of its chemical structure.This definition therefore excludes the organo aminophosphonates, whichhowever may be included in compositions of the invention as heavy metalion sequestrant components.

The organo diphosphonic acid is preferably a C₁-C₄ diphosphonic acid,more preferably a C₂ diphosphonic acid, such as ethylene diphosphonicacid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP)and may be present in partially or fully ionized form, particularly as asalt or complex.

Dispersant Polymer

Preferred compositions herein may additionally contain a dispersantpolymer. When present, a dispersant polymer in the instant compositionsis typically at levels in the range from about 0% to about 25%,preferably from about 0.5% to about 20%, more preferably from about 1%to about 8% by weight of the composition. Dispersant polymers are usefulfor improved filming performance of the present compositions, especiallyin higher pH embodiments, such as those in which wash pH exceeds about9.5. Particularly preferred are polymers which inhibit the deposition ofcalcium carbonate or magnesium silicate on dishware.

Dispersant polymers suitable for use herein are further illustrated bythe film-forming polymers described in U.S. Pat. No. 4,379,080 (Murphy),issued Apr. 5, 1983.

Suitable polymers are preferably at least partially neutralized oralkali metal, ammonium or substituted ammonium (e.g., mono-, di- ortriethanolammonium) salts of polycarboxylic acids. The alkali metal,especially sodium salts are most preferred. While the molecular weightof the polymer can vary over a wide range, it preferably is from about1,000 to about 500,000, more preferably is from about 1,000 to about250,000, and most preferably, especially if the composition is for usein North American automatic dishwashing appliances, is from about 1,000to about 5,000.

Other suitable dispersant polymers include those disclosed in U.S. Pat.No. 3,308,067 issued Mar. 7, 1967, to Diehl. Unsaturated monomeric acidsthat can be polymerized to form suitable dispersant polymers includeacrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconicacid, aconitic acid, mesaconic acid, citraconic acid andmethylenemalonic acid. The presence of monomeric segments containing nocarboxylate radicals such as methyl vinyl ether, styrene, ethylene, etc.is suitable provided that such segments do not constitute more thanabout 50% by weight of the dispersant polymer.

Copolymers of acrylamide and acrylate having a molecular weight of fromabout 3,000 to about 100,000, preferably from about 4,000 to about20,000, and an acrylamide content of less than about 50%, preferablyless than about 20%, by weight of the dispersant polymer can also beused. Most preferably, such dispersant polymer has a molecular weight offrom about 4,000 to about 20,000 and an acrylamide content of from about0% to about 15%, by weight of the polymer.

Particularly preferred dispersant polymers are low molecular weightmodified polyacrylate copolymers. Such copolymers contain as monomerunits: a) from about 90% to about 10%, preferably from about 80% toabout 20% by weight acrylic acid or its salts and b) from about 10% toabout 90%, preferably from about 20% to about 80% by weight of asubstituted acrylic monomer or its salt and have the general formula:—[(C(R²)C(R¹)(C(O)OR³)] wherein the apparently unfilled valencies are infact occupied by hydrogen and at least one of the substituents R¹, R²,or R³, preferably R¹ or R², is a 1 to 4 carbon alkyl or hydroxyalkylgroup; R¹ or R² can be a hydrogen and R³ can be a hydrogen or alkalimetal salt. Most preferred is a substituted acrylic monomer wherein R¹is methyl, R² is hydrogen, and R³ is sodium.

Suitable low molecular weight polyacrylate dispersant polymer preferablyhas a molecular weight of less than about 15,000, preferably from about500 to about 10,000, most preferably from about 1,000 to about 5,000.The most preferred polyacrylate copolymer for use herein has a molecularweight of about 3,500 and is the fully neutralized form of the polymercomprising about 70% by weight acrylic acid and about 30% by weightmethacrylic acid.

Other suitable modified polyacrylate copolymers include the lowmolecular weight copolymers of unsaturated aliphatic carboxylic acidsdisclosed in U.S. Pat. Nos. 4,530,766, and 5,084,535.

Agglomerated forms of the present compositions may employ aqueoussolutions of polymer dispersants as liquid binders for making theagglomerate (particularly when the composition consists of a mixture ofsodium citrate and sodium carbonate). Especially preferred arepolyacrylates with an average molecular weight of from about 1,000 toabout 10,000, and acrylate/maleate or acrylate/fumarate copolymers withan average molecular weight of from about 2,000 to about 80,000 and aratio of acrylate to maleate or fumarate segments of from about 30:1 toabout 1:2. Examples of such copolymers based on a mixture of unsaturatedmono- and dicarboxylate monomers are disclosed in European PatentApplication No. 66,915, published Dec. 15, 1982.

Other dispersant polymers useful herein include the polyethylene glycolsand polypropylene glycols having a molecular weight of from about 950 toabout 30,000 which can be obtained from the Dow Chemical Company ofMidland, Mich. Such compounds for example, having a melting point withinthe range of from about 30° C. to about 100° C., can be obtained atmolecular weights of 1,450, 3,400, 4,500, 6,000, 7,400, 9,500, and20,000. Such compounds are formed by the polymerization of ethyleneglycol or propylene glycol with the requisite number of moles ofethylene or propylene oxide to provide the desired molecular weight andmelting point of the respective polyethylene glycol and polypropyleneglycol. The polyethylene, polypropylene and mixed glycols are referredto using the formula:HO(CH₂CH₂O)_(m)(CH₂CH(CH₃)O)_(n)(CH(CH₃)CH₂O)_(o)OH wherein m, n, and oare integers satisfying the molecular weight and temperaturerequirements given above.

Yet other dispersant polymers useful herein include the cellulosesulfate esters such as cellulose acetate sulfate, cellulose sulfate,hydroxyethyl cellulose sulfate, methylcellulose sulfate, andhydroxypropylcellulose sulfate. Sodium cellulose sulfate is the mostpreferred polymer of this group.

Also suitable are the cellulosic derivatives, such as cellulose acetate,cellulose, hydroxyethyl cellulose, methylcellulose,hydroxypropylcellulose and carboxy methyl cellulose. These dispersantpolymers also have the added advantage that they also reduce spottingand filming on hydrophobic surfaces such as plastic.

Other suitable dispersant polymers are the carboxylated polysaccharides,particularly starches, celluloses and alginates, described in U.S. Pat.No. 3,723,322, Diehl, issued Mar. 27, 1973; the dextrin esters ofpolycarboxylic acids disclosed in U.S. Pat. No. 3,929,107, Thompson,issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch esters,oxidized starches, dextrins and starch hydrolysates described in U.S.Pat No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylatedstarches described in U.S. Pat. No. 3,629,121, Eldib, issued Dec. 21,1971; and the dextrin starches described in U.S. Pat. No. 4,141,841,McDonald, issued Feb. 27, 1979. Preferred cellulose-derived dispersantpolymers are the carboxymethyl celluloses.

Yet another group of acceptable dispersants are the organic dispersantpolymers, such as polyaspartate.

Polymeric Soil Release Agent

Known polymeric soil release agents, hereinafter “SRA” or “SRA's”, canoptionally be employed in the present tablet compositions. If utilized,SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1%to 5%, preferably from 0.2% to 3.0% by weight, of the composition.

Preferred SRA's typically have hydrophilic segments to hydrophilize thesurface of hydrophobic fibers such as polyester and nylon, andhydrophobic segments to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles therebyserving as an anchor for the hydrophilic segments. This can enablestains occurring subsequent to treatment with SRA to be more easilycleaned in later washing procedures. Alternatively, in an automaticdishwashing compositions, these hydrophobically modified polymers act toprevent redeposition on to hydrophobic surfaces, such as plastic, andprovide the additional benefit of improved spotting and filming onhydrophobic surfaces. The most suitable polymers for these applicationsare the hydrophobically modified polyacrylates.

SRA's can include a variety of charged, e.g., anionic or even cationic(see U.S. Pat. No. 4,956,447), as well as noncharged monomer units andstructures may be linear, branched or even star-shaped. They may includecapping moieties which are especially effective in controlling molecularweight or altering the physical or surface-active properties. Structuresand charge distributions may be tailored for application to differentfiber or textile types and for varied detergent or detergent additiveproducts.

Preferred SRA's include oligomeric terephthalate esters, typicallyprepared by processes involving at least onetransesterification/oligomerization, often with a metal catalyst such asa titanium(IV) alkoxide. Such esters may be made using additionalmonomers capable of being incorporated into the ester structure throughone, two, three, four or more positions, without of course forming adensely crosslinked overall structure.

Suitable SRA's include: a sulfonated product of a substantially linearester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and allyl-derivedsulfonated terminal moieties covalently attached to the backbone, forexample as described in U.S. Pat. No. 4,968,451, Nov. 6, 1990 to J. J.Scheibel and E. P. Gosselink: such ester oligomers can be prepared by(a) ethoxylating allyl alcohol, (b) reacting the product of (a) withdimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in atwo-stage transesterification/oligomerization procedure and (c) reactingthe product of (b) with sodium metabisulfite in water; the nonionicend-capped 1,2-propylene/polyoxyethylene terephthalate polyesters ofU.S. Pat. No. 4,711,730, Dec. 8, 1987 to Gosselink et al, for examplethose produced by transesterification/oligomerization ofpoly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol)(“PEG”); the partly- and fully-anionic-end-capped oligomeric esters ofU.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomersfrom ethylene glycol (“EG”), PG, DMT andNa-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped blockpolyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987to Gosselink, for example produced from DMT, Me-capped PEG and EG and/orPG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896; Oct. 31,1989 to Maldonado, Gosselink et al, the latter being typical of SRA'suseful in both laundry and fabric conditioning products, an examplebeing an ester composition made from m-sulfobenzoic acid monosodiumsalt, PG and DMT optionally but preferably further comprising added PEG,e.g., PEG 3400.

SRA's also include simple copolymeric blocks of ethylene terephthalateor propylene terephthalate with polyethylene oxide or polypropyleneoxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosicderivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; and the C₁-C₄ alkylcelluloses and C₄ hydroxyalkylcelluloses; see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al.Suitable SRA's characterised by poly(vinyl ester) hydrophobe segmentsinclude graft copolymers of poly(vinyl ester), e.g., C₁-C₆ vinyl esters,preferably poly(vinyl acetate), grafted onto polyalkylene oxidebackbones. See European Patent Application 0 219 048, published Apr. 22,1987 by Kud, et al. Commercially available examples include SOKALANSRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA'sare polyesters with repeat units containing 10-15% by weight of ethyleneterephthalate together with 90-80% by weight of polyoxyethyleneterephthalate, derived from a polyoxyethylene glycol of averagemolecular weight 300-5,000. Commercial examples include ZELCON 5126 fromDupont and MILEASE T from ICI.

Another preferred SRA is an oligomer having empirical formula(CAP)₂(EG/PG)₅(T)₅(SIP)₁ which comprises terephthaloyl (T),sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG)units and which is preferably terminated with end-caps (CAP), preferablymodified isethionates, as in an oligomer comprising onesulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy andoxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 toabout 10:1, and two end-cap units derived from sodium2-(2-hydroxyethoxy)-ethanesulfonate. Said SRA preferably furthercomprises from 0.5% to 20%, by weight of the oligomer, of acrystallinity-reducing stabilizer, for example an anionic surfactantsuch as linear sodium dodecylbenzenesulfonate or a member selected fromxylene-, cumene-, and toluene- sulfonates or mixtures thereof, thesestabilizers or modifiers being introduced into the synthesis pot, all astaught in U.S. Pat. No. 5,415,807, Gosselink, Pan, Kellett and Hall,issued May 16, 1995. Suitable monomers for the above SRA include Na2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na-dimethyl5-sulfoisophthalate, EG and PG.

Yet another group of preferred SRA's are oligomeric esters comprising:(1) a backbone comprising (a) at least one unit selected from the groupconsisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit whichis at least trifunctional whereby ester linkages are formed resulting ina branched oligomer backbone, and combinations thereof; (b) at least oneunit which is a terephthaloyl moiety; and (c) at least one unsulfonatedunit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more cappingunits selected from nonionic capping units, anionic capping units suchas alkoxylated, preferably ethoxylated, isethionates, alkoxylatedpropanesulfonates, alkoxylated propanedisulfonates, alkoxylatedphenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferredof such esters are those of empirical formula:

{(CAP)x(EG/PG)y′(DEG)y″(PEG)y′″(T)z(SIP)z′(SEG)q(B)m}

wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG)represents di(oxyethylene)oxy units; (SEG) represents units derived fromthe sulfoethyl ether of glycerin and related moiety units; (B)represents branching units which are at least trifunctional wherebyester linkages are formed resulting in a branched oligomer backbone; xis from about 1 to about 12; y′ is from about 0.5 to about 25; y″ isfrom 0 to about 12; y′″ is from 0 to about 10; y′+y″+y′″totals fromabout 0.5 to about 25; z is from about 1.5 to about 25; z′ is from 0 toabout 12; z+z′ totals from about 1.5 to about 25; q is from about 0.05to about 12; m is from about 0.01 to about 10; and x, y′, y″, y′″, z,z′, q and m represent the average number of moles of the correspondingunits per mole of said ester and said ester has a molecular weightranging from about 500 to about 5,000.

Preferred SEG and CAP monomers for the above esters includeNa-2-(2-,3-dihydroxypropoxy)ethanesulfonate (“SEG”), Na-2-{2-(2-hydroxyethoxy) ethoxy} ethanesulfonate (“SE3”) and its homologsand mixtures thereof and the products of ethoxylating and sulfonatingallyl alcohol. Preferred SRA esters in this class include the product oftransesterifying and oligomerizing sodium2-{2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or sodium2-[2-{2-(2-hydroxyethoxy)-ethoxy} ethoxy]ethanesulfonate, DMT, sodium2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using anappropriate Ti(IV) catalyst and can be designated as(CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is(Na+—O₃S[CH₂CH₂O]3.5)— and B is a unit from glycerin and the mole ratioEG/PG is about 1.7:1 as measured by conventional gas chromatographyafter complete hydrolysis.

Additional classes of SRA's include (I) nonionic terephthalates usingdiisocyanate coupling agents to link up polymeric ester structures, seeU.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918Lagasse et al; (II) SRA's with carboxylate terminal groups made byadding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With a proper selection of catalyst, thetrimellitic anhydride forms linkages to the terminals of the polymerthrough an ester of the isolated carboxylic acid of trimelliticanhydride rather than by opening of the anhydride linkage. Eithernonionic or anionic SRA's may be used as starting materials as long asthey have hydroxyl terminal groups which may be esterified. See U.S.Pat. No. 4,525,524 Tung et al.; (III) anionic terephthalate-based SRA'sof the urethane-linked variety, see U.S. Pat. No. 4,201,824, Violland etal; (IV) poly(vinyl caprolactam) and related co-polymers with monomerssuch as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate,including both nonionic and cationic polymers, see U.S. Pat. No.4,579,681, Ruppert et al.; (V) graft copolymers, in addition to theSOKALAN types from BASF made, by grafting acrylic monomers on tosulfonated polyesters; these SRA's assertedly have soil release andanti-redeposition activity -similar to known cellulose ethers: see EP279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomerssuch as acrylic acid and vinyl acetate on to proteins such as caseins,see EP 457,205 A to BASF (1991); (VII) polyester-polyamide SRA'sprepared by condensing adipic acid, caprolactam, and polyethyleneglycol, especially for treating polyamide fabrics, see Bevan et al, DE2,335,044 to Unilever N. V., 1974. Other useful SRA's are described inU.S. Pat. Nos. 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Clay Soil Removal/Anti-redeposition Agents

The compositions of the present invention can also optionally containwater-soluble ethoxylated amines having clay soil removal andantiredeposition properties. Granular compositions which contain thesecompounds typically contain from about 0.01% to about 10.0% by weight ofthe water-soluble ethoxylates amines; liquid detergent compositionstypically contain about 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein. See U.S. Pat. No. 4,891,160, VanderMeer, issuedJan. 2, 1990 and WO 95/32272, published Nov. 30, 1995. Another type ofpreferred antiredeposition agent includes the carboxy methyl cellulose(CMC) materials. These materials are well known in the art.

Corrosion Inhibitor Compound

The detergent tablets of the present invention suitable for use indishwashing methods may contain corrosion inhibitors preferably selectedfrom organic silver coating agents, particularly paraffin,nitrogen-containing corrosion inhibitor compounds and Mn(II) compounds,particularly Mn(II) salts of organic ligands.

Organic silver coating agents are described in PCT Publication No.WO94/16047 and copending European application No. EP-A-690122.Nitrogen-containing corrosion inhibitor compounds are disclosed incopending European Application no. EP-A-634,478. Mn(II) compounds foruse in corrosion inhibition are described in copending EuropeanApplication No. EP-A-672 749.

Organic silver coating agent, when present, may be incorporated at alevel of preferably from about 0.05% to about 10%, more preferably fromabout 0.1% to about 5% by weight of the total composition.

The functional role of the silver coating agent is to form ‘in use’ aprotective coating layer on any silverware components of the washload towhich the compositions of the invention are being applied. The silvercoating agent should hence have a high affinity for attachment to solidsilver surfaces, particularly when present in as a component of anaqueous washing and bleaching solution with which the solid silversurfaces are being treated.

Suitable organic silver coating agents herein include, but are notlimited to, fatty esters of mono- or polyhydric alcohols having fromabout 1 to about 40 carbon atoms in the hydrocarbon chain.

The fatty acid portion of the fatty ester can be obtained from mono- orpoly-carboxylic acids having from about 1 to about 40 carbon atoms inthe hydrocarbon chain. Suitable examples of monocarboxylic fatty acidsinclude behenic acid, stearic acid, oleic acid, palmitic acid, myristicacid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyricacid, Valerie acid, lactic acid, glycolic acid andβ,β-dihydroxyisobutyric acid. Examples of suitable polycarboxylic acidsinclude: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid,malic acid and succinic acid.

The fatty alcohol radical in the fatty ester can be represented by mono-or polyhydric alcohols having from about 1 to about 40 carbon atoms inthe hydrocarbon chain. Examples of suitable fatty alcohols include;behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol,glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol,sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.

Preferably, the fatty acid and/or fatty alcohol group of the fatty esteradjunct material have from about 1 to about 24 carbon atoms in the alkylchain.

Preferred fatty esters herein are ethylene glycol, glycerol and sorbitanesters wherein the fatty acid portion of the ester normally comprises aspecies selected from behenic acid, stearic acid, oleic acid, palmiticacid or myristic acid.

The glycerol esters are also highly preferred. These are the mono-, di-or tri-esters of glycerol and the fatty acids as defined above.

Specific examples of fatty alcohol esters for use herein include:stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate,oleyl dimaleate, and tallowyl proprionate. Some fatty acid esters usefulherein include: xylitol monopalmitate, pentaerythritol monostearate,sucrose monostearate, glycerol monostearate, ethylene glycolmonostearate, sorbitan esters. Suitable sorbitan esters include sorbitanmonostearate, sorbitan palmitate, sorbitan monolaurate, sorbitanmonomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitandilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate,and also mixed tallowalkyl sorbitan mono- and di-esters.

Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate,glycerol monobehenate, and glycerol distearate are preferred glycerolesters herein.

Suitable organic silver coating agents include triglycerides, mono ordiglycerides, and wholly or partially hydrogenated derivatives thereof,and any mixtures thereof. Suitable sources of fatty acid esters includevegetable and fish oils and animal fats. Suitable vegetable oils includesoy bean oil, cotton seed oil, castor oil, olive oil, peanut oil,safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil andcorn oil.

Waxes, including microcrystalline waxes are suitable organic silvercoating agents herein. Preferred waxes have a melting point in the rangefrom about 35° C. to about 110° C. and comprise generally from about 12to about 70 carbon atoms. Preferred are petroleum waxes of the paraffinand microcrystalline type which are composed of long-chain saturatedhydrocarbon compounds.

Alginates and gelatin are suitable organic silver coating agents whichcan be used in the compositions herein.

Dialkyl amine oxides such as about C₁₂ to about C₂₀ methylamine oxide,and dialkyl quaternary ammonium compounds and salts, such as the aboutC₁₂ to about C₂₀ methylammonium halides are also suitable.

Other suitable organic silver coating agents include certain polymericmaterials. Polyvinylpyrrolidones with an average molecular weight offrom about 12,000 to about 700,000, polyethylene glycols (PEG) with anaverage molecular weight of from about 600 to about 10,000, polyamineN-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,and cellulose derivatives such as methylcellulose,carboxymethylcellulose and hydroxyethylcellulose are examples of suchpolymeric materials.

Certain perfume materials, particularly those demonstrating a highsubstantivity for metallic surfaces, are also useful as the organicsilver coating agents herein.

Polymeric soil release agents can also be used as an organic silvercoating agent.

A preferred organic silver coating agent is a paraffin oil, typically apredominantly branched aliphatic hydrocarbon having a number of carbonatoms in the range of from about 20 to about 50; preferred paraffin oilselected from predominantly branched C₂₅₋₄₅ species with a ratio ofcyclic to noncyclic hydrocarbons of from about 1:10 to about 2:1,preferably from about 1:5 to about 1:1. A paraffin oil meeting thesecharacteristics, having a ratio of cyclic to noncyclic hydrocarbons ofabout 32:68, is sold by Wintershall, Salzbergen, Germany, under thetrade name WINOG 70.

Suitable nitrogen-containing corrosion inhibitor compounds includeimidazole and derivatives thereof such as benzimidazole, 2-heptadecylimidazole and those imidazole derivatives described in Czech Patent No.139, 279 and British Patent GB-A-1,137,741, which also discloses amethod for making imidazole compounds.

Also suitable as nitrogen-containing corrosion inhibitor compounds arepyrazole compounds and their derivatives, particularly those where thepyrazole is substituted in any of the 1, 3, 4 or 5 positions bysubstituents R₁, R₃, R₄ and R₅ where R₁ is any of H, CH₂OH, CONH₃, orCOCH₃, R₃ and R₅ are any of C₁-C₂₀ alkyl or hydroxyl, and R₄ is any ofH, NH₂ or NO₂.

Other suitable nitrogen-containing corrosion inhibitor compounds includebenzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine,stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole andindazole.

Nitrogen-containing compounds such as amines, especially distearylamineand ammonium compounds such as ammonium chloride, ammonium bromide,ammonium sulphate or diammonium hydrogen citrate are also suitable.

The detergent tablets may contain an Mn(II) corrosion inhibitorcompound. The Mn(II) compound is preferably incorporated at a level offrom about 0.005% to about 5% by weight, more preferably from about0.01% to about 1%, most preferably from about 0.02% to about 0.4% byweight of the compositions. Preferably, the Mn(II) compound isincorporated at a level to provide from about 0.1 ppm to about 250 ppm,more preferably from about 0.5 ppm to about 50 ppm, even more preferablyfrom about 1 ppm to about 20 ppm by weight of Mn(II) ions in anybleaching solution.

The Mn (II) compound may be an inorganic salt in anhydrous, or anyhydrated forms. Suitable salts include manganese sulphate, manganesecarbonate, manganese phosphate, manganese nitrate, manganese acetate andmanganese chloride. The Mn(II) compound may be a salt or complex of anorganic fatty acid such as manganese acetate or manganese stearate.

The Mn(II) compound may be a salt or complex of an organic ligand. Inone preferred aspect the organic ligand is a heavy metal ionsequestrant. In another preferred aspect the organic ligand is a crystalgrowth inhibitor.

Other suitable additional corrosion inhibitor compounds include,mercaptans and diols, especially mercaptans with about 4 to about 20carbon atoms including lauryl mercaptan, thiophenol, thionapthol,thionalide and thioanthranol. Also suitable are saturated or unsaturatedC₁₀-C₂₀ fatty acids, or their salts, especially aluminium tristearate.The C₁₂-C₂₀ hydroxy fatty acids, or their salts, are also suitable.Phosphonated octa-decane and other anti-oxidants such asbetahydroxytoluene (BHT) are also suitable.

Copolymers of butadiene and maleic acid, particularly those suppliedunder the trade reference no. 07787 by Polysciences Inc. have been foundto be of particular utility as corrosion inhibitor compounds.

Another preferred active detergent component for use in the presentinvention is a hydrocarbon oil, typically a predominantly long chain,aliphatic hydrocarbons having a number of carbon atoms in the range offrom about 20 to about 50; preferred hydrocarbons are saturated and/orbranched; preferred hydrocarbon oil selected from predominantly branchedC₂₅₋₄₅ species with a ratio of cyclic to noncyclic hydrocarbons of fromabout 1:10 to about 2:1, preferably from about 1:5 to about 1:1. Apreferred hydrocarbon oil is paraffin. A paraffin oil meeting thecharacteristics as outlined above, having a ratio of cyclic to noncyclichydrocarbons of about 32:68, is sold by Wintershall, Salzbergen,Germany, under the trade name WTNOG 70.

The detergent tablets of the present invention suitable for use indishwashing methods may contain a water-soluble bismuth compound,preferably present at a level of from about 0.005% to about 20%, morepreferably from about 0.01% to about 5%, even more preferably from about0.1% to about 1% by weight of the compositions.

The water-soluble bismuth compound may be essentially any salt orcomplex of bismuth with essentially any inorganic or organic counteranion. Preferred inorganic bismuth salts are selected from the bismuthtrihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate andcitrate are preferred salts with an organic counter anion.

Colorant

The term ‘colorant’, as used herein, means any substance that absorbsspecific wavelengths of light from the visible light spectrum. Suchcolorants when added to a detergent composition have the effect ofchanging the visible color and thus the appearance of the detergentcomposition. Colorants may be for example either dyes or pigments.Preferably the colorants are stable in composition in which they are tobe incorporated. Thus in a composition of high pH the colorant ispreferably alkali stable and in a composition of low pH the colorant ispreferably acid stable.

The compressed and/or non-compressed, non-encapsulating portions maycontain a colorant, a mixture of colorants, colored particles or mixtureof colored particles such that the compressed portion and thenon-compressed, non-encapsulating portion have different visualappearances. Preferably one of either the compressed portion or thenon-compressed, non-encapsulating portion a colorant.

Where the non-compressed, non-encapsulating portion comprises two ormore compositions of active detergent components, preferably at leastone of either the first and second and/or subsequent compositionscomprises a colorant. Where both the first and second and/or subsequentcompositions comprise a colorant it is preferred that the colorants havea different visual appearance.

Where present the coating layer preferably comprises a colorant. Wherethe compressed portion and the coating layer comprise a colorant, it ispreferred that the colorants provide a different visual effect.

Examples of suitable dyes include reactive dyes, direct dyes, azo dyes.Preferred dyes include phthalocyanine dyes, anthraquinone dye, quinolinedyes, monoazo, disazo and polyazo. More preferred dyes includeanthraquinone, quinoline and monoazo dyes. Preferred dyes includeSANDOLAN E-HRL 180% (tradename), SANDOLAN MILLING BLUE (tradename),TURQUOISE ACID BLUE (tradename) and SANDOLAN BRILLIANT GREEN (tradename)all available from Clariant UK, HEXACOL QUINOLINE YELLOW (tradename) andHEXACOL BRILLIANT BLUE (tradename) both available from Pointings, UK,ULTRA MARINE BLUE (tradename) available from Holliday or LEVAFIXTURQUISE BLUE EBA (tradename) available from Bayer, USA.

Furthennore, it is preferred that the colorant does not cause visiblestaining to plastic, such as an automatic dishwasher or plastictableware, after a plurality of cycles, more preferably between 1 and 50cycles.

The colorant may be incorporated into the compressed and/ornon-compressed, non-encapsulating portion by any suitable method.Suitable methods include mixing all or selected active detergentcomponents with a colorant in a drum or spraying all or selected activedetergent components with the colorant in a rotating drum.Alternatively, the colorants color may be improved by predisolving thecolorant in a compatible solvent prior to addition of the colorant tothe composition.

Colorant when present as a component of the compressed portion ispresent at a level of from about 0.001% to about 1.5%, preferably fromabout 0.01% to about 1.0%, most preferably from about 0.1% to about0.3%. When present as a component of the gel portion, colorant isgenerally present at a level of from about 0.001% to about 0.1%, morepreferably from about 0.005% to about 0.05%, most preferably from about0.007% to about 0.02%. When present as a component of the coating layer,colorant is present at a level of from about 0.01% to about 0.5%, morepreferably from about 0.02% to about 0.1%, most preferably from about0.03% to about 0.06%, by weight.

Silicone and Phosphate Ester Suds Suppressors

The compositions of the invention can optionally contain an alkylphosphate ester suds suppressor, a silicone suds suppressor, orcombinations thereof. Levels in general are from about 0% to about 10%,preferably, from about 0.001% to about 5%. However, generally (for costconsiderations and/or deposition) preferred compositions herein do notcomprise suds suppressors or comprise suds suppressors only at lowlevels, e.g., less than about 0.1% of active suds suppressing agent.

Silicone suds suppressor technology and other defoaming agents usefulherein are extensively documented in “Defoaming, Theory and IndustrialApplications”, Ed., P. R. Garrett, Marcel Dekker, N.Y., 1973, ISBN0-8247-8770-6, incorporated herein by reference. See especially thechapters entitled “Foam control in Detergent Products” (Ferch et al) and“Surfactant Antifoams” (Blease et al). See also U.S. Pat. Nos. 3,933,672and 4,136,045. Highly preferred silicone suds suppressors are thecompounded types known for use in laundry detergents such as heavy-dutygranules, although types hitherto used only in heavy-duty liquiddetergents may also be incorporated in the instant compositions. Forexample, polydimethylsiloxanes having trimethylsilyl or alternateendblocking units may be used as the silicone. These may be compoundedwith silica and/or with surface-active nonsilicon components, asillustrated by a suds suppressor comprising 12% silicone/silica, 18%stearyl alcohol and 70% starch in granular form. A suitable commercialsource of the silicone active compounds is Dow Corning Corp.

If it is desired to use a phosphate ester, suitable compounds aredisclosed in U.S. Pat. No. 3,314,891, issued Apr. 18, 1967, to Schmolkaet al, incorporated herein by reference. Preferred alkyl phosphateesters contain from 16-20 carbon atoms. Highly preferred alkyl phosphateesters are monostearyl acid phosphate or monooleyl acid phosphate, orsalts thereof, particularly alkali metal salts, or mixtures thereof.

It has been found preferable to avoid the use of simplecalcium-precipitating soaps as antifoams in the present compositions asthey tend to deposit on the dishware. Indeed, phosphate esters are notentirely free of such problems and the formulator will generally chooseto minimize the content of potentially depositing antifoams in theinstant compositions.

Enzyme Stabilizing System

Preferred enzyme-containing compositions herein may comprise from about0.001% to about 10%, more preferably from about 0.005% to about 8%, evenmore preferably from about 0.01% to about 6%, by weight of an enzymestabilizing system. The enzyme stabilizing system can be any stabilizingsystem which is compatible with the detersive enzyme. Such stabilizingsystems can comprise calcium ion, boric acid, propylene glycol, shortchain carboxylic acid, boronic acid, chlorine bleach scavengers andmixtures thereof. Such stabilizing systems can also comprise reversibleenzyme inhibitors, such as reversible protease inhibitors. For othersuitable enzyme stabilizer and systems see Severson, U.S. Pat. No.4,537,706.

Lime Soap Dspersant Compound

The compositions of active detergent components may contain a lime soapdispersant compound, preferably present at a level of from about 0.1% toabout 40% by weight, more preferably about 1% to about 20% by weight,most preferably from about 2% to about 10% by weight of thecompositions.

A lime soap dispersant is a material that prevents the precipitation ofalkali metal, ammonium or amine salts of fatty acids by calcium ormagnesium ions. Preferred lime soap dispersant compounds are disclosedin PCT Application No. WO93/08877.

Suds Suppressing System

The detergent tablets of the present invention, when formulated for usein machine washing compositions, preferably comprise a suds suppressingsystem present at a level of from about 0.01% to about 15%, preferablyfrom about 0.05% to about 10%, most preferably from about 0.1% to about5% by weight of the composition.

Suitable suds suppressing systems for use herein may compriseessentially any known antifoam compound, including, for example siliconeantifoam compounds, 2-alkyl and alkanol antifoam compounds. Preferredsuds suppressing systems and antifoam compounds are disclosed in PCTApplication No. WO93/08876 and EP-A-705 324.

Polymeric Dye Transfer Inhibiting Agents

The detergent tablets herein may also comprise from about 0.01% to about10%, preferably from about 0.05% to about 0.5% by weight of polymericdye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selectedfrom polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof

Optical Brightener

The detergent tablets suitable for use in laundry washing methods asdescribed herein, also optionally contain from about 0.005% to about 5%by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those having thestructural formula:

wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4′-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Clay Softening System

The detergent tablets suitable for use in laundry cleaning methods maycontain a clay softening system comprising a clay mineral compound andoptionally a clay flocculating agent.

The clay mineral compound is preferably a smectite clay compound.Smectite clays are disclosed in the U.S. Pat. Nos. 3,862,058, 3,948,790,3,954,632 and 4,062,647. European Patents Nos. EP-A-299,575 andEP-A-313,146 in the name of the Procter and Gamble Company describesuitable organic polymeric clay flocculating agents.

Cationic Fabric Softening Agents

Cationic fabric softening agents can also be incorporated intocompositions in accordance with the present invention which are suitablefor use in methods of laundry washing. Suitable cationic fabricsoftening agents include the water insoluble tertiary amines or dilongchain amide materials as disclosed in GB-A-1514 276 and EP-B-0 011 340.

Cationic fabric softening agents are typically incorporated at totallevels of from about 0.5% to about 15% by weight, normally from about 1%to about 5% by weight.

Adjunct Materials

Detersive ingredients or adjuncts optionally included in the instantcompositions can include one or more materials for assisting orenhancing cleaning performance, treatment of the substrate to becleaned, processing aids, or designed to improve the aesthetics of thecompositions. Adjuncts which can also be included in compositions of thepresent invention, at their conventional art-established levels for use(preferably, adjunct materials comprise, in total, from about 30% toabout 99.9%, preferably from about 70% to about 95%, by weight of thecompositions), include other active ingredients such as color speckles,fillers, germicides, hydrotropes, anti-oxidants, perfumes, solubilizingagents, carriers and processing aids.

Depending on whether a greater or lesser degree of compactness isrequired, filler materials can also be present in the instantcompositions. These include sucrose, sucrose esters, sodium sulfate,potassium sulfate, etc., in amounts up to about 70%, preferably fromabout 0% to about 40% of the composition. Preferred filler is sodiumsulfate, especially in good grades having at most low levels of traceimpurities.

Sodium sulfate used herein preferably has a purity sufficient to ensureit is non-reactive with bleach; it may also be treated with low levelsof sequestrants, such as phosphonates or EDDS in magnesium-salt form.Note that preferences, in terms of purity sufficient to avoiddecomposing bleach, applies also to pH-adjusting component ingredients,specifically including any silicates used herein.

The detergent tablets can also can contain processing aids which canassist in the production of the detergent tablets. For example, thecompressed body portion can contain a tableting aid, such as stearicacid, to increase the ease of removal of the compressed body portionfrom the dyes of a tablet press.

Hydrotrope materials such as sodium benzene sulfonate, sodium toluenesulfonate, sodium cumene sulfonate, etc., can be present, e.g., forbetter dispersing surfactant.

Bleach-stable perfumes (stable as to odor); and bleach-stable dyes suchas those disclosed in U.S. Pat. No. 4,714,562, Roselle et al, issuedDec. 22, 1987 can also be added to the present compositions inappropriate amounts.

Since the compositions herein can contain water-sensitive ingredients oringredients which can co-react when brought together in an aqueousenvironment, it is desirable to keep the free moisture content at aminimum, e.g., preferably about 7% or less, more preferably 5% or lessof the compositions; and to provide packaging which is substantiallyimpermeable to water and carbon dioxide. Coating measures have beendescribed herein to illustrate a way to protect the ingredients fromeach other and from air and moisture. Plastic bottles, includingrefillable or recyclable types, as well as conventional barrier cartonsor boxes are another helpful means of assuring maximum shelf-storagestability. As noted, when ingredients are not highly compatible, it mayfurther be desirable to coat at least one such ingredient with alow-foaming nonionic surfactant for protection. There are numerous waxymaterials which can readily be used to form suitable coated particles ofany such otherwise incompatible components; however, the formulatorprefers those materials which do not have a marked tendency to depositor form films on dishes including those of plastic construction.

Form of Composition.

The detergent tablet can be of any conceivable form size or shape.Preferably, the size is selected for ease of storage, ease of use andsuch that the tablet will fit into any dispensing devices used incleaning, e.g. the detergent dispenser in an automatic dishwashingmachine.

The detergent tablet, non-compressed, gelatinous body, and the pluralityof non-compressed, gelatinous portions can be regular or irregular inshape. They can be any regular or irregular geometric forms such as,concave, convex, cubic, spheroidal, frustum of a cone (a section of acone), rectangular prismic, cylindrical, disc, pyramodial, tetrahedral,dodecahedral, octahedral, conical, ellipsoidal, figure eight, orrhombohedral. See CRC Standard Mathematical Tables, 26th Ed, Dr. WilliamH. Beyer Editor, pages 127, 128 and 276 to 278. They can even belettering, symbols, caricatures, trademarks, images, such as corporatelogos, cartoon characters, team logos or mascots. It is also be possibleto have a two or more non-compressed, gelatinous portions of differentshapes such that when these plurality of non-compressed, gelatinousportion are combined to make a tablet, the tablet is in the shape of apicture or symbol, such as a flag, a crest or an emblem could be made.The use of different compatible colorants and dyes in the differentnon-compressed, gelatinous portions is also possible and would result ina more accurate representation of logos, flags etc. The list of possibleshapes and combinations is endless.

When any part of the tablet has straight edges it is preferred thateither the edges be chamfered or rounded. These edges can be in eitheror both of the compressed solid body portion and/or the at least onemould. Additionally, when part of the tablet has corners, it ispreferred that the corners be rounded.

Process

As described in detail herein before, the non-compressed, gelatinousbody, and the plurality of non-compressed, gelatinous portions comprisesat least one active detergent component. The active detergent component,thickening system and any other ingredients in the non-compressed,gelatinous body, or any one of the plurality of non-compressed,gelatinous portions are pre-mixed using any known suitable mixingequipment. Once prepared, the non-compressed, gelatinous body, or anyone of the plurality of non-compressed, gelatinous portions is deliveredas a flowable, pumpable gel in metered amounts. The gel portion is thenallowed to harden or thicken on the compressed body portion. Anyadditional, non-compressed, gelatinous portions are mixed separately,and delivered as a flowable, pumpable gel in metered amounts.

The detergent tablets may be employed in any conventional domesticwashing process wherein detergent tablets are commonly employed,including but not limited to automatic dishwashing and fabriclaundering.

Machine Dishwashing Method

Any suitable methods for machine washing or cleaning soiled tablewareare envisaged.

A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, silverware, metallic items,cutlery and mixtures thereof, with an aqueous liquid having dissolved ordispensed therein an effective amount of a detergent tablet in accordwith the invention. By an effective amount of the detergent tablet it ismeant from 8 g to 60 g of product dissolved or dispersed in a washsolution of volume from 3 to 10 liters, as are typical product dosagesand wash solution volumes commonly employed in conventional machinedishwashing methods. Preferably the detergent tablets are from 15 g to40 g in weight, more preferably from 20 g to 35 g in weight.

Laundry Washing Method

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent tablet composition in accord with the invention. By aneffective amount of the detergent tablet composition it is meant from 40g to 300 g of product dissolved or dispersed in a wash solution ofvolume from 5 to 65 liters, as are typical product dosages and washsolution volumes commonly employed in conventional machine laundrymethods.

In a preferred use aspect a dispensing device is employed in the washingmethod. The dispensing device is charged with the detergent product, andis used to introduce the product directly into the drum of the washingmachine before the commencement of the wash cycle. Its volume capacityshould be such as to be able to contain sufficient detergent product aswould normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensingdevice containing the detergent product is placed inside the drum. Atthe commencement of the wash cycle of the washing machine water isintroduced into the drum and the drum periodically rotates. The designof the dispensing device should be such that it permits containment ofthe dry detergent product but then allows release of this product duringthe wash cycle in response to its agitation as the drum rotates and alsoas a result of its contact with the wash water.

To allow for release of the detergent product during the wash the devicemay possess a number of openings through which the product may pass.Alternatively, the device may be made of a material which is permeableto liquid but impermeable to the solid product, which will allow releaseof dissolved product. Preferably, the detergent product will be rapidlyreleased at the start of the wash cycle thereby providing transientlocalized high concentrations of product in the drum of the washingmachine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a waythat container integrity is maintained in both the dry state and duringthe wash cycle.

Alternatively, the dispensing device may be a flexible container, suchas a bag or pouch. The bag may be of fibrous construction coated with awater impermeable protective material so as to retain the contents, suchas is disclosed in European published Patent Application No. 0018678.Alternatively it may be formed of a water-insoluble synthetic polymericmaterial provided with an edge seal or closure designed to rupture inaqueous media as disclosed in European published Patent Application Nos.0011500, 0011501, 0011502, and 0011968. A convenient form of waterfrangible closure comprises a water soluble adhesive disposed along andsealing one edge of a pouch formed of a water impermeable polymeric filmsuch as polyethylene or polypropylene.

EXAMPLES

The following non limiting examples further illustrate the presentinvention. The exemplified compositions include both automaticdishwashing and laundry compositions.

Abbreviations Used in Examples

In the detergent compositions, the abbreviated component identificationshave the following meanings:

STPP : Sodium tripolyphosphate Citrate : Tri-sodium citrate dihydrateBicarbonate : Sodium hydrogen carbonate Citric Acid : Anhydrous Citricacid Carbonate : Anhydrous sodium carbonate Silicate : Amorphous SodiumSilicate (SiO₂:Na₂O ratio = 1.6-3.2) Metasilicate : Sodium metasilicate(SiO₂:Na₂O ratio = 1.0) PB1 : Anhydrous sodium perborate monohydrate PB4: Sodium perborate tetrahydrate of nominal formula NaBO₂.3H₂O.H₂O₂ TAED: Tetraacetyl ethylene diamine Plurafac : C₁₃-C₁₅ mixedethoxylated/propoxylated fatty alcohol with an average degree ofethoxylation of 3.8 and an average degree of propoxylation of 4.5, soldunder the tradename Plurafac by BASF Tergitol : Nonionic surfactantavailable under the tradename Tergitol 15S9 from Union Carbide SLF18 :Epoxy-capped poly(oxyalkylated) alcohol of Example III of WO 94/22800wherein 1,2- epoxydodecane is substituted for 1,2-epoxydecane availableunder the tradename Polytergent SLF18D from OLIN. HEDP : Ethane1-hydroxy-1,1-diphosphonic acid DETPMP : Diethyltriamine penta(methylene) phosphonate, marketed by monsanto under the tradenameDequest 2060 PAAC : Pentaamine acetate cobalt (III) salt BzP : BenzoylPeroxide Paraffin : Paraffin oil sold under the tradename Winog 70 byWintershall. Protease : Proteolytic enzyme Amylase : Amylolytic enzyme.480N : Random copolymer of 7:3 acrylate/methacrylate, average molecularweight 3,500 Sulphate : Anhydrous sodium sulphate. PEG 3000 :Polyethylene Glycol molecular weight approximately 3000 available fromHoechst PEG 6000 : Polyethylene Glycol molecular weight approximately6000 available from Hoechst Castorwax.rtm. : A hydrogenated castor oilSugar : Household sucrose Gelatine : Gelatine Type A, 65 bloom strengthavailable from Sigma CMC : Carboxymethylcellulose Dodecandioic Acid :C12 dicarboxylic acid Adipic Acid : C6 dicarboxylic acid Lauric Acid :C12 monocarboxylic acid BTA : Benzotriazole PA30 : Polyacrylic acid ofaverage molecular weight approximately 4,500 Crosslinked PA :Crosslinked polyacrylic acid of average molecular weight approximatelygreater than 5000 pH : Measured as a 1% solution in distilled water at20° C.

Example 1

A detergent tablet according to the present invention may be prepared asfollows. A gel matrix formulation as disclosed in Example 2, formulationA is prepared. The proper amount of non-aqueous solvent is provided to amixer and 5 shear is applied to the solvent at a moderate rate(2,500-5,000 rpm). The proper amount of gelling agent is gradually addedto the solvent under shear conditions until the mixture is homogeneous.The shear rate of the mixture is gradually increased to high shearcondition of around 10,000 rpm. The temperature of the mixture isincreased to between 55° C. and 60° C. The shear is then stopped and the10 mixture is allowed to cool to temperatures between 35° C. and 45° C.Using a low shear mixer, the remaining ingredients are then added to themixture as solids. The final mixture is then metered into a mould of thedesired shape and allowed to stand until the gel hardens or is no longerflowable.

Example 2

Detergent Tablets according to the present invention may be formulatedas follows:

A B C D E F STPP 21.40 26.00 26.00 — 25.00 19.10 Citrate — — — 13.2 — —Carbonate 7.70 7.00 7.00 — 9.20 7.50 Silicate 6.30 7.40 7.50 13.20 2.505.05 Protease¹ 6.40 4.00 5.00 2.25 4.00 2.00 Amylase² 0.46 0.36 0.360.30 1.00 0.43 PB1 6.30 6.25 6.25 0.73 7.85 5.50 PB4 — — — 3.46 — —Nonionic 0.88 0.75 1.00 0.75 0.25 0.88 PAAC — 0.008 — 0.006 — 0.004 TAED— — — 2.17 0.65 — HEDP — — — 0.34 — 0.46 DETPMP — — — 0.33 — — Paraffin— 0.25 0.25 0.21 — — BTA — 0.15 0.15 0.12 — — PA30 — — — 1.6 — —Sulphate — — — 12.03 3.50 11.04 Bicarbonate 12.00 6.50 5.75 6.50 3.00Citric acid 9.00 6.50 5.75 7.00 3.00 Dipropyleneglycol — — 25.00 20.00 —17.00 butylether Glycerol Triacetate 17.00 20.00 — — 24.00 — ThixatrolST ® — — 2.50 3.50 2.00 — Polyethylene glycol³ 2.00 1.00 — — — 1.50Metasilicate — — — 3.50 — 20.50 Silicate — 5.50 — — 14.00 — Misc./waterto balance Q.S Q.S Q.S Q.S Q.S Q.S Weight (g) 20.00 20.00 20.50 20.0025.00 30.00 ¹Protease enzyme can be either Savinase ® or as disclosed inU.S. Pat. No. 5,677,272. ²Amylase enzyme can be as disclosed in NovoNordisk application PCT/DK96/00056 now WO 96/23873 and is obtained froman alkalophilic Bacillus species having a N-terminal sequence of:His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp,or Termamyl ®. ³MW 4,000-8,000.

Example 3

The following illustrates examples detergent tablets of the presentinvention suitable for use in a dishwashing machine.

A detergent tablet according to the present invention may be prepared asfollows. A first gel portion formulation as disclosed in Example 3,formulation G is prepared. The proper amount of non-aqueous solvent isprovided to a mixer and shear is applied to the solvent at a moderaterate (2,500-5,000 rpm). The proper amount of gelling agent is graduallyadded to the solvent under shear conditions until the mixture ishomogeneous. The shear rate of the mixture is gradually increased tohigh shear condition of around 10,000 rpm. The temperature of themixture is increased to between 55° C. and 60° C. The shear is thenstopped and the mixture is allowed to cool to temperatures between 40°C. and 45° C. Using a low shear mixer, the remaining ingredients arethen added to the mixture as solids. The final mixture is then meteredinto a mould of the desired shape and allowed to stand until the gelhardens or is no longer flowable. A second gel portion which has beenprepared in the same fashion as the first portion is then added to themould and allowed to stand until the gel hardens or is no longerflowable. Finally when both gel portions have hardened or are no longerflowable, the tablet is coated with a coating layer.

G H I J K L First gel portion STPP — 42.00 37.00 35.00 40.00 25.00Citrate 15.00 — — — — — Carbonate — 12.00 12.00 16.00 11.00 15.50Silicate 30.00 11.00 11.00 10.00 3.50 10.00 Protease¹ — — — 1.00 — —Amylase² — — 0.001 0.46 1.0 0.75 PB1 1.5 8.00 6.10 9.00 10.00 6.50 PB45.00 — — — — — Nonionic 1.00 0.75 1.20 2.00 0.25 1.30 PAAC — 0.008 0.0160.006 — 0.004 TAED 4.00 — — — 0.65 — HEDP 0.50 — — — — 0.46 DETPMP 0.60— — — — — Paraffin 0.50 0.50 0.50 0.70 0.25 — BTA 0.50 0.30 0.30 0.200.30 — PA30 2.00 — — — — — Sulphate 15.00 — 2.00 — 7.00 20.00Dipropyleneglycol — — 25.00 20.00 — 17.00 butylether Glycerol Triacetate17.00 20.00 — — 24.00 — Thixatrol ST ® — — 2.50 3.50 2.00 — Polyethyleneglycol³ 2.00 1.00 — — — 1.50 Misc./water to balance q.s. q.s. q.s. q.s.q.s. q.s. Weight (g) 12.0 3.0 3.0 3.0 6.0 5.0 Second gel portionProtease¹ 10.00 4.55 6.45 6.00 0.50 11.50 Amylase² 5.00 8.55 3.00 9.0013.50 0.50 Metasilicate — 45.00 — 35.10 25.00 45.00 Bicarbonate — 9.5015.02 9.00 5.00 12.00 Citric acid — 9.50 9.50 10.00 5.00 12.00 BzP — — —6.00 — — Citrate 30.00 — — — 25.00 — Silicate 35.00 — 38.03 — — —Dipropyleneglycol — — 25.00 20.00 — 17.00 butylether Glycerol Triacetate17.00 20.00 — — 24.00 — Thixatrol ST ® — — 2.50 3.50 2.00 — Polyethyleneglycol³ 2.00 1.00 — — — 1.50 Misc./water to balance q.s. q.s. q.s. q.s.q.s. q.s. Weight (g) 15.0 3.0 3.0 3.0 6.0 5.0 Coating Layer Dodecandioicacid — 90.00 82.00 — — 90.00 Adipic acid — — — 92.00 — — Lauric acid — —8.00 — — — Starch 15.00 10.00 10.00 8.0 — 10.00 PEG — — — — 100 — Weight(g) 1.00 1.00 1.20 0.80 0.50 1.00 Total weight (g) of tablet 25 g 25 g20 g 30 g 18 g 35 g ¹Protease enzyme can be either Savinase ® or asdisclosed in U.S. Pat. No. 5,677,272. ²Amylase enzyme can be asdisclosed in Novo Nordisk application PCT/DK96/00056 now WO 96/23873 andis obtained from an alkalophilic Bacillus species having a N-terminalsequence of:His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp,or Termamyl ®. ³MW 4,000-8,000.

Example 4

M N O P Q R First Gel portion STPP — 42.00 37.00 35.00 40.00 25.00Citrate 15.00 — — — — — Carbonate — 11.00 12.00 16.00 11.00 15.50Silicate 30.00 12.00 11.00 10.00 3.50 10.00 Protease¹ — — — 1.00 — —Amylase² — — 0.001 0.46 1.0 0.75 PB1 1.5 7.00 6.10 9.00 10.00 6.50 PB45.00 — — — — — Nonionic 1.00 0.75 1.20 2.00 0.25 1.30 PAAC — 0.008 0.0160.006 — 0.004 TAED 4.00 — — — 0.65 — HEDP 0.50 — — — — 0.46 DETPMP 0.60— — — — — Paraffin 0.50 0.50 0.50 0.70 0.25 — BTA 0.50 0.30 0.30 0.200.30 — PA30 2.00 — — — — — Crosslinked PA — 2.2 — — — — Sulphate 15.00 —2.00 — 7.00 20.00 Dipropyleneglycol — — 25.00 20.00 — 17.00 butyletherGlycerol Triacetate 17.00 20.00 — — 24.00 — Thixatrol ST ® — — 2.50 3.502.00 — Polyethylene glycol³ 2.00 1.00 — — — 1.50 Misc./water to balanceq.s. q.s. q.s. q.s. q.s. q.s. Weight (g) 20.0 g 20.0 g 20.0 g 20.0 g 22g 30.0 g Second gel portion Tergitol — — 21.5 18.92 — — PEG 3000 89.40 —— — — — PEG 6000 86.9 — — — — BzP 10.60 11.00 — — 20.00 20.00 Sugar — —53.4 29.04 65.00 65.00 Gelatine — — 15.01 30.00 5.00 5.00 Starch — — —10.00 — — Water — — 10.00 10.00 10.00 10.00 Misc./balance q.s. q.s. q.s.q.s. q.s. q.s. Weight (g) 2.5 g 5.0 g 2.5 g 2.5 g 3 g 3 g Third gelportion Tergitol — — 21.5 18.92 — — Dipropyleneglycol — 45.00 — — — —butylether Glycerol Triacetate 30.00 — — — — — Thixatrol ST ® — 33.00 —— — — Polyethylene glycol³ 50.00 — — — — — BzP 10.60 11.00 — — 20.0020.00 Sugar — — 53.4 29.04 65.00 65.00 Gelatine — — 15.01 30.00 5.005.00 Starch — — — 10.00 — — Water — — 10.00 10.00 10.00 10.00Misc./balance q.s. q.s. q.s. q.s. q.s. q.s. Weight (g) 2.5 g 5.0 g 2.5 g2.5 g 3 g 3 g Total weight (g) of tablet 22.5 g 25 g 22.5 g 22.5 g 25 g33 g ¹Protease enzyme can be either Savinase ® or as disclosed in U.S.Pat. No. 5,677,272. ²Amylase enzyme can be as disclosed in Novo Nordiskapplication PCT/DK96/00056 now WO 96/23873 and is obtained from analkalophilic Bacillus species having a N-terminal sequence of:His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp,or Termamyl ®. ³MW 4,000-8,000.

What is claimed is:
 1. A detergent tablet comprising, a non-compressed,gelatinous body which comprises: i) a first non-compressed, gelatinousportion, said first gelatinous portion comprising a thickening systemand at least one detergent active; and ii) a second non-compressed,gelatinous portion, said second gelatinous portion comprising athickening system and at least one detergent active; wherein thethickening system in (i) and (ii) comprises a mixture of a non-aqueousdiluent and a gelling agent; wherein said first gelatinous portion isformulated so that at least about 80% of said detergent active isdelivered to the wash within the first 5 minutes of a domestic washprocess; and wherein the release of said detergent active in said secondgelatinous portion is delayed by at least five minutes.
 2. The detergenttablet according to claim 1 wherein said frist gelatinous portion isformulated so that at least about 90% of said detergent active isdelivered to the wash within the first 3 minutes of a domestic washprocess.
 3. The detergent tablet according to claim 1 wherein saiddetergent active is selected from the group consisting of surfactants,enzymes, bleaching agents, disrupting agents, effervescing agents,silver care agents, builders, silicates, pH control agents or buffers,and mixtures thereof.
 4. The detergent tablet according to claim 1wherein said gelatinous body further includes a structure modifyingagent.
 5. A detergent tablet according claim 1 wherein said detergenttablet has a shape selected from the group consisting of, concave,convex, cubic, rectangular prismic, cylindrical, spheroidal, frustum ofa cone, disc, pyramodial, tetrahedral, dodecahedral, octahedral,conical, ellipsoidal, figure eight, and rhombohedral.
 6. A detergenttablet according to claim 1 wherein said detergent tablet has at leasttwo non-compressed, gelatinous portions and the release of saiddetergent active in one of said non-compressed, gelatinous portions isdelayed until after wash rinse cycle.
 7. A method of washing tablewarein a domestic automatic dishwashing appliance, said method comprisingtreating the soiled tableware in an automatic dishwasher with saiddetergent tablet according to claim
 1. 8. A method of laundering fabricsaid method comprising treating the fabric with said detergent tabletaccording to claim
 1. 9. A detergent tablet comprising a non-compressed,gelatinous body comprising a plurality of non-compressed, gelatinousportions, wherein each gelatinous portion comprises a thickening systemand at least one detergent active; wherein the thickening systemcomprises a mixture of a non-aqueous diluent and a gelling agent;wherein at least one of said plurality of non-compressed, gelatinousportions is formulated so that at least about 80% of said detergentactive is delivered to the wash within the first 5 minutes of a domesticwash process; and wherein the release of said detergent active in one ofsaid non-compressed, gelatinous portion is delayed by at least fiveminutes.
 10. The detergent tablet according to claim 9 wherein saiddetergent active is selected from the group consisting of surfactants,enzymes, bleaching agents, disrupting agents, effervescing agents,silver care agents, builders, silicates, pH control agents or buffers,and mixtures thereof.
 11. A detergent tablet according to claim 9wherein said detergent tablet has at least two non-compressed,gelatinous portions and the release of said detergent active in one ofsaid non-compressed, gelatinous portions is delayed by at least sevenminutes.